Non-aqueous electrolyte secondary battery

ABSTRACT

The present invention provides a non-aqueous electrolyte secondary battery having an anode active material with a high capacity and excellent cycle characteristics. The active material comprises a salt of a metal or a semi-metal and a compound selected from the group consisting of oxo-acids, thiocyanic acid, cyanogen, and cyanic acid, wherein each said oxo-acid comprises an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates.

BACKGROUND OF THE INVENTION

The present invention relates to an improvement in anodes of non-aqueous electrolyte secondary batteries.

Non-aqueous electrolyte secondary batteries including lithium or a lithium compound for the anode are expected to have a high voltage and high energy density, and therefore, they are extensively studied.

Known cathode active materials for the non-aqueous electrolyte secondary batteries are oxides and chalcogens of transition metals, such as LiMn₂ O₄, LiCoO₂, LiNiO₂, V₂ O₅, Cr₂ O₅, MnO₂, TiS₂, MoS₂ and the like. These compounds have a layered or tunneled crystal structure to allow lithium ions to freely intercalate and deintercalate. The use of metallic lithium for the anode active material has intensively been examined. Such use, however, has a drawback; lithium dendrite occurring on the surface of metallic lithium in the course of charging results in lowering the charge-discharge efficiency and may come into contact with the cathode to cause an inner short circuit.

In order to solve this problem, the potentials for application of lithium alloys, such as lithium-aluminum, which can depress the growth of lithium dendrite and absorb and desorb lithium, for the anode have been studied. However, when lithium alloys are used for the anode, repeated charge and discharge causes pulverization of the alloys, posing a problem of poor cycle life characteristics.

There are proposals for solving this problem by inhibiting pulverization of the alloys by including additional elements in the lithium-aluminum alloy (for example, Japanese Laid-Open Patent Publication Sho 62-119856 and Hei 4-109562), although the improvement is not sufficient. Lithium ion batteries recently developed have anodes composed of carbon material that reversibly intercalates and deintercalates lithium and has excellent cycle characteristics and safety though having a smaller capacity than those of the anode active materials mentioned above.

With a view to enhancing the capacity, a number of studies have proposed application of oxides for the anode; for example, crystalline oxides, such as SnO and SnO₂ (Japanese Laid-Open Patent Publication Hei 7-122274 and Hei 7-235293) and amorphous oxides, such as SnSiO₃, SnSi_(1-x) P_(x) O₃ (Japanese Laid-Open Patent Publication Hei 7-288123). These oxides, however, do not sufficiently improve the characteristics.

SUMMARY OF THE INVENTION

The object of the present invention is thus to provide an anode for non-aqueous electrolyte secondary batteries having excellent charge-discharge cycle characteristics.

The present invention provides an anode that absorbs lithium in the course of charging not to cause dendrite and has a large electric capacity and an excellent cycle life.

The present invention is directed to a non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, the anode having an active material that comprises a salt of a metal or a semi-metal and a compound selected from the group consisting of an oxo-acid, thiocyanic acid, cyanogen, and cyanic acid, wherein the oxo-acid is one of an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium.

It is preferable that the metal or the semi-metal constituting the metal salt or the semi-metal salt is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb. Especially preferable are Sn, Pb, In, and Bi.

The present invention gives a non-aqueous electrolyte secondary battery that is free from a short circuit due to dendrite and has a high energy density, an excellent cycle life, and a high reliability.

While the novel features of the invention are set forth particularly in the appended claims, the invention, both as to organization and content, will be better understood and appreciated, along with other objects and features thereof, from the following detailed description taken in conjunction with the drawings.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a vertical sectional view schematically illustrating a test cell used for evaluating the electrode characteristics of active materials in accordance with the present invention.

FIG. 2 is a vertical sectional view schematically illustrating a cylindrical battery including an anode in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

As discussed above, the anode of the present invention comprises a metal salt or a semi-metal salt of a specific acid or cyanogen.

In the following description, salts of a divalent metal M^(II) are given as examples. Salts of nitrogen oxo-acids include nitrates M^(II) (NO₃)₂ and nitrites M^(II) (NO₂)₂.

Salts of sulfur oxo-acids include sulfates M^(II) SO₄, sulfites M^(II) SO₃, disulfates M^(II) S₂ O₇, peroxomonosulfates M^(II) SO₅, peroxodisulfates M^(II) S₂ O₈, thiosulfates M^(II) S₂ O₃, disulfites M^(II) S₂ O₅, thiosulfites M^(II) S₂ O₂, hydrogensulfates such as M^(II) (HSO₄)₂, thionates such as dithionates M^(II) S₂ O₆ and dithionites M^(II) S₂ O₄, sulfoxylates such as M^(II) SO₂, and hydrogen-containing acid salts.

Preferable salts of phosphorus oxo-acids include hydrogenphosphates such as M^(II) HPO₄ and M^(II) (H₂ PO₄)₂, phosphinates M^(II) (PH₂ O₂)₂, and phosphonates M^(II) PHO₃.

Salts of carbon oxo-acids include carbonates M^(II) CO₃ and hydrogencarbonates M^(II) (HCO₃)₂.

Preferable salts of boron oxo-acids include hydrogenborates such as M^(II) (H₂ BO₃)₂ and M^(II) HBO₃.

Salts of selenium oxo-acids include selenates M^(II) SeO₄, selenites M^(II) SeO₃, M^(II) SeO₅, hydrogenselenates M^(II) (HSeO₄)₂, and hydrogenselenites M^(II) (HSeO₃)₂.

Salts of tellurium oxo-acids include tellurates such as M^(II) ₃ TeO₆ and M_(II) TeO₄, and hydrogentellurates such as M^(II) ₅ (H₅ TeO₆)₂, M^(II) ₂ H₂ TeO₆, M^(II) ₃ (H₃ TeO₆)₂, and M^(II) H₄ TeO₆.

Available thiocyanates include M^(II) (SCN)₂, while available cyanides and cyanates include M^(II) (CN)₂ and M^(II) (ONC)₂.

The metal salt and the semi-metal salt of the present invention are, however, not restricted to the above chemical compositions.

Among the above salts, sulfates, hydrogensulfates, carbonates, hydrogenborates, and hydrogenphosphates are preferable for the improvement in cycle characteristics.

The following gives salts of oxo-acids of transition elements W, Mo, Ti, Zr, Nb, Ta, Mn, and V as examples. In the following formulae, M^(III) represents a trivalent metal or semi-metal.

Available tungstates include M^(II) WO₄, M^(II) WO₃, M^(III) WO₆. Available molybdates include M^(II) MoO₄ and M^(III) Mo₄ O₆. Available titanates include M^(II) TiO₃, M^(II) TiO₄, (M^(III))₂ TiO₅, and M^(II) Ti₃ O₇.

Available zirconates include M^(II) ZrO₃ and M^(II) ZrO₄. Available chromates include M^(III) CrO₃, M^(II) CrO₄, M^(II) Cr₂ O₄, and (M^(III))₂ CrO₆. Available niobates include M^(III) NbO₄, M^(II) Nb₂ O₆, and (M^(III))₂ Nb₂ O₇.

Available tantalates include M^(III) TaO₄ and (M^(II))₂ Ta₂ O₇. Available manganates include M^(II) MnO₃, (M^(III))₂ MnO₄, and (M^(III))₂ MnO₆. Available vanadates include M^(III) VO₄, (M^(III))₂ VO₅, and M^(II) V₂ O₆.

Preferable are chromates, tungstates, molybdates, vanadates, manganates, and tantalates, and especially preferable are chromates, tungstates, and molybdates for the improvement in cycle characteristics.

The metal salt and the semi-metal salt of the present invention are, however, not restricted to the above chemical compositions.

The present inventors have made an intensive study on the availability of various metal salts and semi-metal salts as the negative electrode material. It was found that such compounds can serve as the negative electrode materials with a high capacity and exceptional cycle life characteristics that have a crystal structure in which the metal or semi-metal is surrounded by a) the salts including oxygen and any one of nitrogen, sulfur, phosphorus, carbon, boron, selenium, and tellurium, such as salts of oxo-acids of nitrogen, sulfur, phosphorus, carbon, boron, selenium and tellurium or by the salts further including hydrogen such as hydrogen-containing oxo-acids; b) cyanides containing nitrogen and carbon; c) cyanates containing nitrogen, carbon and oxygen; or d) thiocyanates containing nitrogen, carbon and sulfur and in which those salts are bonded to the metal or semi-metal by ionic force.

The present inventors also discovered that such compounds can also serve as the negative electrode materials with a high capacity and superb cycle life characteristics that have a crystal structure in which the metal or semi-metal is surrounded by the salts of oxo-acid of a transition element including oxygen and any one of tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese and vanadium, that is, tungstates, molybdates, titanates, zirconates, chromates, niobates, tantalates, manganates and vanadates.

The prior art metal oxides have the greater tendency of covalent bonding and tougher skeletons than those of the metal salts and semi-metal salts in accordance with the present invention. While the prior art metal oxides are presumed to be relatively brittle under the conditions of expansion and contraction accompanied by intercalation and deintercalation of a large amount of lithium, however, the metal salts and semi-metal salts of the present invention are expected to be relatively tough under the conditions of expansion and contraction accompanied by intercalation and deintercalation of a large amount of lithium. It is also found that the existence of hydrogen in the salts of oxo-acids further improves the cycle characteristics, although the details have not yet been elucidated.

The chemical compositions of the metal salts and the semi-metal salts discussed above represent only examples of divalent or trivalent metals and semi-metals. Chemical compositions of metal salts and semi-metal salts of different valences should be apparent to the skilled in the art. For example, selenates can be expressed by the following general formulae as the metal salts and semi-metal salts of the valence m:

M₂ (SeO₄)_(m), M₂ (SeO₃)_(m), M₂ (SeO₅)_(m), M(HSeO₄)_(m), and M(HSeO₃)_(m).

Some examples in accordance with the present invention are given below, although the anode material of the present invention is not restricted to the chemical compositions discussed in these examples.

EXAMPLE 1

Test cells shown in FIG. 1 were manufactured and tested for evaluation of the electrode characteristics of various metal and semi-metal nitrates and nitrites specified in Tables 1 and 2 and used as the anode active material.

Referring to FIG. 1, numeral 1 designates a test electrode composed of a molded mixture containing an active material. The test electrode 1 is arranged on the substantial center of a battery casing 2. A separator 3 of a micro-porous polypropylene film was placed on the test electrode 1. After injection of an electrolyte solution, the opening of the battery casing 2 is sealed with a sealing plate 6 having a counter electrode 4 composed of a metallic lithium disc of 17.5 mm in diameter on the inner surface thereof and a polypropylene gasket 5 on the circumference thereof. This completes a test cell.

The mixture included 6 g of an active material powder, 3 g of graphite powder as a conductive agent, and 1 g of polyethylene powder as a binding agent. The test electrode 1 was obtained by press molding 0.1 g of the mixture to a disc of 17.5 mm in diameter. The electrolyte used was prepared by dissolving lithium perchlorate (LiClO₄) at a concentration of 1 mol/l in a 1:1 mixed solution (volume ratio) of ethylene carbonate and dimethoxyethane.

At a constant electric current of 2 mA, the test cell was subjected to cathode polarization (which corresponds to charging in case that the active material-containing electrode is considered as the anode) until the electrode potential became 0 V with respect to the lithium counter electrode. The test cell was then subjected to anode polarization (which corresponds to discharging) until the electrode potential became 1.5 V with respect to the counter electrode. After the repeated cathode polarization and anode polarization, and the electrode characteristics were evaluated.

For the purpose of comparison, electrodes were manufactured in the above manner using the known compounds shown in Table 3, that is, crystalline oxides WO₂, Fe₂ O₃, SnO, and PbO, sulfides SnS and PbS, and amorphous metal oxides SnSiO₃ and SnSi₀.8 P₀.2 O₃.1, and test cells were assembled and tested under the same conditions for evaluation of the electrode characteristics.

Tables 1 through 3 show the discharge capacities per one gram of the active material in the first cycle.

The measurement proved that all the test cells of Example 1 were capable of being charged and discharged. After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 1.

The above experiments show that cathode polarization makes lithium absorbed in the electrodes including the active materials of Example 1 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium. The electrodes of Example 1 have higher capacities than those of the comparative examples.

Cylindrical batteries shown in FIG. 2 were manufactured and tested for evaluation of the cycle characteristics of the batteries using various metal and semi-metal nitrates and nitrites of Example 1.

Each battery was manufactured in the following manner.

A cathode active material LiMn₁.8 Co₀.2 O₄ was prepared by mixing Li₂ CO₃, Mn₃ O₄, and CoCO₃ at a predetermined molar ratio, heating the mixture at 900° C., and classifying the mixture to or below 100 meshes.

A paste was prepared by mixing 100 g of the cathode active material, 10 g of carbon powder as a conductive agent, and 8 g (as the resin) of aqueous dispersion of polyethylene tetrafluoride as a binding agent, and pure water. The paste was applied onto a titanium core member, dried, and rolled out to a cathode plate.

An anode plate was manufactured by mixing a metal or semi-metal nitrate or nitrite as an active material, graphite powder as a conductive agent, and Teflon powder as a binding agent at the weight ratio of 60:30:10, adding a petroleum solvent to the mixture to yield a paste, applying the paste onto a copper core member, and drying it at 100° C. A micro-porous polypropylene film was used as a separator.

A cathode plate 11 with a cathode lead 14 which is composed of the same material as that of the core member and attached to the cathode plate 11 by spot welding, an anode plate 12 with an anode lead 15 welded thereto, and a separator 13 having a greater width than those of these electrode plates 11 and 12 were wound in spirals to constitute an electrode group. Polypropylene insulating plates 16 and 17 were placed on the top and bottom of the electrode group, and the assembly was inserted into a battery casing 18. After formation of a step on the upper portion of the battery casing 18 and injection of the same non-aqueous electrolyte as that of the above-mentioned test cell, the battery casing 18 was sealed with a sealing plate 19 having an anode terminal 20. This completes a battery.

The batteries constructed as above were subjected to a charge-discharge cycle test at a temperature of 30° C. and a charge-discharge current of 1 mA/cm² in a charge-discharge voltage range of 4.3 V to 2.6 V. A rate of the discharge capacity at the 100-th cycle to the discharge capacity at the second cycle (hereinafter referred to as capacity maintenance rate) was measured.

Anode plates were prepared and test batteries were assembled in the above manner for the comparative examples. The cycle characteristics of the comparative examples were also evaluated under the same conditions.

Tables 1 through 3 show the results of evaluation.

                  TABLE 1                                                          ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al(NO.sub.3).sub.3                                                                        284           75                                                    Al(NO.sub.2).sub.3                                                                        326           73                                                    Sn(NO.sub.3).sub.4                                                                        346           86                                                    Sn(NO.sub.2).sub.4                                                                        389           84                                                    Sn(NO.sub.3).sub.2                                                                        485           84                                                    Sn(NO.sub.2).sub.2                                                                        510           82                                                    Si(NO.sub.3).sub.4                                                                        390           83                                                    Si(NO.sub.2).sub.4                                                                        435           84                                                    Pb(NO.sub.3).sub.2                                                                        356           83                                                    Pb(NO.sub.2).sub.2                                                                        394           82                                                    Cd(NO.sub.3).sub.2                                                                        320           78                                                    Cd(NO.sub.2).sub.2                                                                        336           77                                                    Bi(NO.sub.3).sub.3                                                                        298           78                                                    Bi(NO.sub.2).sub.3                                                                        324           75                                                    In(NO.sub.3).sub.3                                                                        346           78                                                    In(NO.sub.2).sub.3                                                                        375           75                                                    Zn(NO.sub.3).sub.2                                                                        289           75                                                    Zn(NO.sub.2).sub.2                                                                        326           79                                                    Ga(NO.sub.3).sub.3                                                                        335           75                                                    Ga(NO.sub.2).sub.3                                                                        362           72                                                    Ge(NO.sub.3).sub.4                                                                        367           74                                                    Ge(NO.sub.2).sub.4                                                                        400           72                                                    Mg(NO.sub.3).sub.2                                                                        296           81                                                    Mg(NO.sub.2).sub.2                                                                        334           79                                                    Sb(NO.sub.3).sub.3                                                                        425           75                                                    Sb(NO.sub.2).sub.3                                                                        433           73                                                    Ti(NO.sub.3).sub.4                                                                        275           80                                                    V(NO.sub.3).sub.2                                                                         255           84                                                    Cr(NO.sub.2).sub.3                                                                        285           82                                                    Mn(NO.sub.3).sub.2                                                                        263           83                                                    Fe(NO.sub.3).sub.2                                                                        274           81                                                    Co(NO.sub.3).sub.2                                                                        269           80                                                    Ni(NO.sub.3).sub.2                                                                        271           80                                                    Cu(NO.sub.3).sub.2                                                                        265           78                                                    Mo(NO.sub.3).sub.2                                                                        222           77                                                    W(NO.sub.3).sub.4                                                                         215           80                                                    Nb(NO.sub.3).sub.3                                                                        220           79                                                    Ca(NO.sub.3).sub.2                                                                        286           79                                                    Ba(NO.sub.3).sub.2                                                                        275           80                                                    Ir(NO.sub.3).sub.3                                                                        266           81                                                    Sr(NO.sub.3).sub.2                                                                        286           79                                                    ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Ba.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2                                                     425          86                                                  Ca.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2                                                     433          85                                                  Sr.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2                                                     443          85                                                  Mg.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2                                                     435          85                                                  Mn.sub.0.22 Sn.sub.0.78 (NO.sub.3).sub.2                                                     410          86                                                  Fe.sub.0.12 Sn.sub.0.88 (NO.sub.3).sub.2                                                     451          85                                                  Co.sub.0.18 Sn.sub.0.82 (NO.sub.3).sub.2                                                     444          87                                                  Cu.sub.0.18 Sn.sub.0.82 (NO.sub.3).sub.2                                                     435          86                                                  Ti.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2                                                     436          85                                                  Zn.sub.0.12 Sn.sub.0.88 (NO.sub.3).sub.2                                                     442          87                                                  Cr.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2                                                     440          86                                                  Vo.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2                                                     421          87                                                  Ba.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2                                                     312          85                                                  Ca.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2                                                     319          87                                                  Sr.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2                                                     329          87                                                  Mg.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2                                                     326          85                                                  Mn.sub.0.22 Pb.sub.0.78 (NO.sub.3).sub.2                                                     333          84                                                  Fe.sub.0.12 Pb.sub.0.88 (NO.sub.3).sub.2                                                     329          86                                                  Co.sub.0.18 Pb.sub.0.82 (NO.sub.3).sub.2                                                     326          85                                                  Cu.sub.0.18 Pb.sub.0.82 (NO.sub.3).sub.2                                                     319          87                                                  Ti.sub.0.12 Pb.sub.0.82 (NO.sub.3).sub.2                                                     314          81                                                  Zn.sub.0.12 Pb.sub.0.88 (NO.sub.3).sub.2                                                     329          83                                                  Cr.sub.0.12 Pb.sub.0.82 (NO.sub.3).sub.2                                                     320          84                                                  W.sub.0.09 Pb.sub.0.82 (NO.sub.3).sub.2                                                      301          87                                                  Fe.sub.0.18 In.sub.0.88 (NO.sub.3).sub.3                                                     324          82                                                  Co.sub.0.27 In.sub.0.82 (NO.sub.3).sub.3                                                     315          83                                                  Cu.sub.0.27 In.sub.0.82 (NO.sub.3).sub.3                                                     310          84                                                  Ti.sub.0.27 Bi.sub.0.82 (NO.sub.3).sub.3                                                     275          80                                                  Zn.sub.0.27 Bi.sub.0.88 (NO.sub.3).sub.3                                                     284          79                                                  ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                                                   Capacity                                                          Discharge capacity                                                                          maintenance rate                                     Salt         (mAh/g)      (%)                                                  ______________________________________                                         WO.sub.2     190           9                                                   Fe.sub.2 O.sub.3                                                                            185          10                                                   SnO          522           5                                                   SnSiO.sub.3  453          20                                                   PbO          453           2                                                   SnS          498           6                                                   PbS          436           3                                                   SnSi.sub.0.8 P.sub.0.2 O.sub.3.1                                                            406          25                                                   ______________________________________                                    

The batteries using the metal or semi-metal nitrate or nitrite of Example 1 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 2

Test cells discussed in Example 1 were manufactured and tested under the same conditions as those of Example 1 for evaluation of the electrode characteristics of various metal and semi-metal carbonates and hydrogencarbonates specified in Tables 4 and 5 and used as the anode active material. Tables 4 and 5 show the discharge capacities of the test cells in the first cycle.

The measurement proved that all the test cells of Example 2 were capable of being charged and discharged.

After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 2.

The above experiments show that cathode polarization makes lithium absorbed in the electrodes comprising the active materials of Example 2 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium.

Cylindrical batteries discussed in Example 1 were manufactured and tested under the same conditions of those of Example 1 for evaluation of the cycle characteristics of the batteries using various metal and semi-metal carbonates and hydrogencarbonates of Example 2. Tables 4 and 5 show the capacity maintenance rates at the 100-th cycle.

                  TABLE 4                                                          ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (CO.sub.3).sub.3                                                                 342           75                                                    Al(HCO.sub.3).sub.3                                                                       306           86                                                    Sn(CO.sub.3).sub.2                                                                        493           86                                                    SnCO.sub.3 534           82                                                    Sn(HCO.sub.3).sub.4                                                                       424           92                                                    Sn(HCO.sub.3).sub.2                                                                       490           90                                                    Si(CO.sub.3).sub.2                                                                        378           81                                                    Si(HCO.sub.3).sub.4                                                                       365           89                                                    PbCO.sub.3 441           82                                                    Pb(HCO.sub.3).sub.2                                                                       402           84                                                    CdCO.sub.3 397           75                                                    Cd(HCO.sub.3).sub.2                                                                       365           85                                                    Bi.sub.2 (CO.sub.3).sub.3                                                                 369           73                                                    Bi(HCO.sub.3).sub.3                                                                       305           78                                                    In.sub.2 (CO.sub.3).sub.3                                                                 461           76                                                    In(HCO.sub.3).sub.3                                                                       386           85                                                    ZnCO.sub.3 298           72                                                    Zn(HCO.sub.3).sub.2                                                                       268           82                                                    Ga.sub.2 (CO.sub.3).sub.3                                                                 334           73                                                    Sb(HCO.sub.3).sub.3                                                                       315           75                                                    Ga(HCO.sub.3).sub.3                                                                       312           79                                                    Ge(CO.sub.3).sub.2                                                                        365           75                                                    Ge(HCO.sub.3).sub.4                                                                       335           83                                                    MgCO.sub.3 304           79                                                    Mg(HCO.sub.3).sub.2                                                                       292           85                                                    Ti.sub.2 (CO.sub.3).sub.3                                                                 298           75                                                    MnCO.sub.3 263           86                                                    VCO.sub.3  198           86                                                    Cr.sub.2 (CO.sub.3).sub.3                                                                 263           82                                                    FeCO.sub.3 246           84                                                    CoCO.sub.3 259           83                                                    NiCO.sub.3 264           81                                                    CuCO.sub.3 253           82                                                    MoCO.sub.3 221           82                                                    BaCO.sub.3 256           80                                                    CaCO.sub.3 263           75                                                    W(CO.sub.3).sub.2                                                                         215           75                                                    Ir.sub.2 (CO.sub.3).sub.3                                                                 321           73                                                    Sb.sub.2 (CO.sub.3).sub.3                                                                 365           78                                                    Nb(CO.sub.3).sub.5                                                                        187           80                                                    SrCO.sub.3 273           75                                                    ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Ba.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               498          84                                                  Ca.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               485          85                                                  Sr.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               495          85                                                  Mg.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               500          86                                                  Mn.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               482          85                                                  Fe.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               479          87                                                  Co.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               486          86                                                  Cu.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               493          85                                                  Ti.sub.0.2 Sn.sub.0.7 CO.sub.3                                                               475          84                                                  Zn.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               482          85                                                  Cr.sub.0.2 Sn.sub.0.7 CO.sub.3                                                               473          85                                                  Mo.sub.0.2 Sn.sub.0.8 CO.sub.3                                                               459          86                                                  Ba.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               421          83                                                  Ca.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               416          85                                                  Sr.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               416          85                                                  Mg.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               422          84                                                  Mn.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               418          87                                                  Fe.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               409          86                                                  Co.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               417          85                                                  Cu.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               415          84                                                  Ti.sub.0.2 Pb.sub.0.7 CO.sub.3                                                               398          85                                                  Zn.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               405          86                                                  Cr.sub.0.2 Pb.sub.0.7 CO.sub.3                                                               403          85                                                  Mo.sub.0.2 Pb.sub.0.8 CO.sub.3                                                               398          87                                                  (Fe.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3                                               415          79                                                  (Co.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3                                               410          80                                                  (Cu.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3                                               416          81                                                  (Ti.sub.0.2 Bi.sub.0.8).sub.2 (CO.sub.3).sub.3                                               342          78                                                  (Zn.sub.0.3 Bi.sub.0.8).sub.2 (CO.sub.3).sub.3                                               331          77                                                  Ba.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      452          92                                                  Ca.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      441          94                                                  Sr.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      443          94                                                  Mg.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      451          93                                                  Mn.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      443          91                                                  Fe.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      439          92                                                  Co.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      441          91                                                  Cu.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      456          92                                                  Ti.sub.0.2 Sn.sub.0.7 (HCO.sub.3).sub.2                                                      432          92                                                  Zn.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      440          93                                                  Cr.sub.0.2 Sn.sub.0.7 (HCO.sub.3).sub.2                                                      429          94                                                  Mo.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2                                                      420          94                                                  Ba.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      384          88                                                  Ca.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      372          89                                                  Sr.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      372          89                                                  Mg.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      382          87                                                  Mn.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      371          90                                                  Fe.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      367          91                                                  Co.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      371          90                                                  Cu.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      379          89                                                  Ti.sub.0.2 Pb.sub.0.7 (HCO.sub.3).sub.2                                                      352          89                                                  Zn.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      368          90                                                  Cr.sub.0.2 Pb.sub.0.7 (HCO.sub.3).sub.2                                                      369          90                                                  Mo.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2                                                      357          91                                                  Fe.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3                                                      365          86                                                  Co.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3                                                      359          88                                                  Cu.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3                                                      358          87                                                  Ti.sub.0.2 Bi.sub.0.8 (HCO.sub.3).sub.3                                                      301          86                                                  Zn.sub.0.3 Bi.sub.0.8 (HCO.sub.3).sub.3                                                      286          87                                                  ______________________________________                                    

The batteries using the metal or semi-metal carbonate or hydrogencarbonate of Example 2 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogencarbonates has remarkably improved the cycle characteristics.

EXAMPLE 3

The electrode characteristics of various metal and semi-metal hydrogenborates specified in Tables 6 through 8 and used as the anode active material were evaluated in Example 3.

Test cells discussed in Example 1 were manufactured, and the discharge capacities were measured under the same conditions as those of Example 1. The results of measurement are shown in Tables 6 through 8.

The measurement proved that all the test cells of Example 3 were capable of being charged and discharged.

After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 3.

The above experiments show that cathode polarization makes lithium absorbed in the electrodes comprising the active materials of Example 3 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium.

Cylindrical batteries discussed in Example 1 were manufactured, and the capacity maintence rates at the 100-th cycle were measured under the same conditions as those of Example 1. The results of measurement are shown in Tables 6 through 8.

                  TABLE 6                                                          ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (HBO.sub.3).sub.3                                                                 305          78                                                    Al(H.sub.2 BO.sub.3).sub.3                                                                 294          80                                                    SnHBO.sub.3 532          83                                                    Sn(HBO.sub.3).sub.2                                                                        453          85                                                    Sn(H.sub.2 BO.sub.3).sub.4                                                                 405          86                                                    Sn(H.sub.2 BO.sub.3).sub.2                                                                 493          85                                                    Si(HBO.sub.3).sub.2                                                                        326          82                                                    Si(H.sub.2 BO.sub.3).sub.4                                                                 296          83                                                    PbHBO.sub.3 443          84                                                    Pb(H.sub.2 BO.sub.3).sub.2                                                                 421          86                                                    CdHBO.sub.3 328          84                                                    Bi.sub.2 (HBO.sub.3).sub.3                                                                 312          79                                                    Bi(H.sub.2 BO.sub.3).sub.3                                                                 289          81                                                    In.sub.2 (HBO.sub.3).sub.3                                                                 385          84                                                    In(H.sub.2 BO.sub.3).sub.3                                                                 368          86                                                    ZnHBO.sub.3 268          79                                                    Zn(H.sub.2 BO.sub.3).sub.2                                                                 268          81                                                    Ga.sub.2 (HBO.sub.3).sub.3                                                                 338          79                                                    Ga(H.sub.2 BO.sub.3).sub.3                                                                 312          82                                                    Ge(HBO.sub.3).sub.2                                                                        352          85                                                    Ge(H.sub.2 BO.sub.3).sub.4                                                                 335          87                                                    MgHBO.sub.3 296          84                                                    Mg(H.sub.2 BO.sub.3).sub.2                                                                 286          86                                                    ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Sb.sub.2 (HBO.sub.3).sub.3                                                                   310          80                                                  Ba.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              486          84                                                  Ca.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              482          85                                                  Sr.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              482          85                                                  Mg.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              479          84                                                  Zn.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              481          86                                                  Cu.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              469          87                                                  Co.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              467          85                                                  Fe.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              461          86                                                  Ni.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              449          87                                                  Ti.sub.0.2 Sn.sub.0.7 HBO.sub.3                                                              459          86                                                  Cr.sub.0.1 Sn.sub.0.7 HBO.sub.3                                                              449          88                                                  V.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                               429          87                                                  Mo.sub.0.1 Sn.sub.0.9 HBO.sub.3                                                              438          87                                                  W.sub.0.1 Sn.sub.0.8 HBO.sub.3                                                               429          86                                                  (Mn.sub.0.3 In.sub.0.9).sub.2 (HBO.sub.3).sub.3                                              352          82                                                  (Ni.sub.0.3 In.sub.0.8).sub.2 (HBO.sub.3).sub.3                                              357          85                                                  (Co.sub.0.3 In.sub.0.8).sub.3 (HBO.sub.3).sub.3                                              349          85                                                  (Mn.sub.0.3 Bi.sub.0.9).sub.2 (HBO.sub.3).sub.3                                              291          82                                                  (Ni.sub.0.3 Bi.sub.0.8).sub.2 (HBO.sub.3).sub.3                                              281          82                                                  (Co.sub.0.3 Bi.sub.0.8).sub.3 (HBO.sub.3).sub.3                                              279          83                                                  ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                                                   Capacity                                                          Discharge capacity                                                                          maintenance rate                                     Salt         (mAh/g)      (%)                                                  ______________________________________                                         Ba.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             421          88                                                   Ca.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             429          87                                                   Sr.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             429          87                                                   Mg.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             428          88                                                   Zn.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             420          86                                                   Cu.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             419          85                                                   Co.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             425          84                                                   Fe.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             422          85                                                   Ni.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             428          86                                                   Ti.sub.0.2 Pb.sub.0.7 HBO.sub.3                                                             419          89                                                   Cr.sub.0.1 Pb.sub.0.7 HBO.sub.3                                                             401          85                                                   V.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                              398          87                                                   Mo.sub.0.1 Pb.sub.0.9 HBO.sub.3                                                             392          86                                                   W.sub.0.1 Pb.sub.0.8 HBO.sub.3                                                              382          87                                                   ______________________________________                                    

The batteries using the metal or semi-metal hydrogenborates of Example 3 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 4

The electrode characteristics of various salts of oxo-acids of sulfur specified in Tables 9 through 16 and used as the anode active material were evaluated in Example 4.

Tables 9 through 16 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 9                                                          ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (SO.sub.4).sub.3                                                                 389           82                                                    Al.sub.2 (SO.sub.3).sub.3                                                                 405           77                                                    Al.sub.2 (S.sub.2 O.sub.7).sub.3                                                          342           83                                                    Al.sub.2 (SO.sub.5).sub.3                                                                 370           81                                                    Al.sub.2 (S.sub.2 O.sub.8).sub.3                                                          338           85                                                    Al.sub.2 (S.sub.2 O.sub.3).sub.3                                                          375           81                                                    Al.sub.2 (S.sub.2 O.sub.6).sub.3                                                          364           82                                                    Al.sub.2 (S.sub.2 O.sub.5).sub.3                                                          372           83                                                    Al.sub.2 (S.sub.2 O.sub.2).sub.3                                                          378           83                                                    Al.sub.2 (S.sub.2 O.sub.4).sub.3                                                          364           84                                                    Al.sub.2 (SO.sub.2).sub.3                                                                 415           80                                                    Sn(SO.sub.4).sub.2                                                                        482           85                                                    Sn(SO.sub.3).sub.2                                                                        521           80                                                    Sn(S.sub.2 O.sub.7).sub.2                                                                 416           86                                                    Sn(SO.sub.5).sub.2                                                                        456           83                                                    Sn(S.sub.2 O.sub.8).sub.2                                                                 403           84                                                    Sn(S.sub.2 O.sub.3).sub.2                                                                 456           82                                                    Sn(S.sub.2 O.sub.6).sub.2                                                                 423           88                                                    Sn(S.sub.2 O.sub.5).sub.2                                                                 437           87                                                    Sn(S.sub.2 O.sub.2).sub.2                                                                 464           84                                                    Sn(S.sub.2 O.sub.4).sub.2                                                                 424           86                                                    Sn(SO.sub.2).sub.2                                                                        510           82                                                    SnSO.sub.4 532           82                                                    SnSO.sub.3 556           79                                                    SnS.sub.2 O.sub.7                                                                         482           85                                                    SnSO.sub.5 502           83                                                    Al(HSO.sub.4).sub.3                                                                       356           91                                                    Al(HSO.sub.3).sub.3                                                                       375           87                                                    Al(HS.sub.2 O.sub.7).sub.3                                                                320           92                                                    Al(HSO.sub.5).sub.3                                                                       335           91                                                    Al(HS.sub.2 O.sub.8).sub.3                                                                314           89                                                    Al(HS.sub.2 O.sub.3).sub.3                                                                346           88                                                    Al(HS.sub.2 O.sub.6).sub.3                                                                352           89                                                    Al(HS.sub.2 O.sub.5).sub.3                                                                346           90                                                    Al(HS.sub.2 O.sub.2).sub.3                                                                348           91                                                    Al(HS.sub.2 O.sub.4).sub.3                                                                334           92                                                    Al(HSO.sub.2).sub.3                                                                       358           89                                                    Sn(HSO.sub.4).sub.4                                                                       446           95                                                    Sn(HSO.sub.3).sub.4                                                                       453           92                                                    Sn(HS.sub.2 O.sub.7).sub.4                                                                386           94                                                    Sn(HSO.sub.5).sub.4                                                                       423           93                                                    Sn(HS.sub.2 O.sub.8).sub.4                                                                379           94                                                    Sn(HS.sub.2 O.sub.3).sub.4                                                                433           93                                                    Sn(HS.sub.2 O.sub.6).sub.4                                                                402           97                                                    Sn(HS.sub.2 O.sub.5).sub.4                                                                410           96                                                    Sn(HS.sub.2 O.sub.2).sub.4                                                                439           94                                                    Sn(HS.sub.2 O.sub.4).sub.4                                                                403           95                                                    Sn(HSO.sub.2).sub.4                                                                       470           90                                                    Sn(HSO.sub.4).sub.2                                                                       486           93                                                    Sn(HSO.sub.3).sub.2                                                                       496           88                                                    Sn(HS.sub.2 O.sub.7).sub.2                                                                450           92                                                    Sn(HSO.sub.5).sub.2                                                                       457           91                                                    ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         SnS.sub.2 O.sub.8                                                                         460           86                                                    SnS.sub.2 O.sub.3                                                                         505           79                                                    SnS.sub.2 O.sub.6                                                                         476           85                                                    SnS.sub.2 O.sub.5                                                                         483           85                                                    SnS.sub.2 O.sub.2                                                                         536           80                                                    SnS.sub.2 O.sub.4                                                                         497           81                                                    SnSO.sub.2 545           79                                                    Si(SO.sub.4).sub.2                                                                        395           85                                                    Si(SO.sub.3).sub.2                                                                        411           82                                                    Si(S.sub.2 O.sub.7).sub.2                                                                 341           87                                                    Si(SO.sub.5).sub.2                                                                        362           85                                                    Si(S.sub.2 O.sub.8).sub.2                                                                 322           87                                                    Si(S.sub.2 O.sub.3).sub.2                                                                 375           84                                                    Si(S.sub.2 O.sub.6).sub.2                                                                 332           85                                                    Si(S.sub.2 O.sub.5).sub.2                                                                 343           84                                                    Si(S.sub.2 O.sub.2).sub.2                                                                 378           82                                                    Si(S.sub.2 O.sub.4).sub.2                                                                 350           85                                                    Si(SO.sub.2).sub.2                                                                        421           83                                                    PbSO.sub.4 452           84                                                    PbSO.sub.3 472           83                                                    PbS.sub.2 O.sub.7                                                                         405           86                                                    PbSO.sub.5 432           85                                                    PbS.sub.2 O.sub.8                                                                         400           86                                                    PbS.sub.2 O.sub.3                                                                         441           84                                                    PbS.sub.2 O.sub.6                                                                         411           85                                                    PbS.sub.2 O.sub.5                                                                         419           85                                                    PbS.sub.2 O.sub.2                                                                         445           82                                                    PbS.sub.2 O.sub.4                                                                         412           84                                                    Sn(HS.sub.2 O.sub.8).sub.2                                                                426           93                                                    Sn(HS.sub.2 O.sub.3).sub.2                                                                472           91                                                    Sn(HS.sub.2 O.sub.6).sub.2                                                                436           94                                                    Sn(HS.sub.2 O.sub.5).sub.2                                                                440           94                                                    Sn(HS.sub.2 O.sub.2).sub.2                                                                471           91                                                    Sn(HS.sub.2 O.sub.4).sub.2                                                                446           93                                                    Sn(HSO.sub.2).sub.2                                                                       492           90                                                    Si(HSO.sub.4).sub.4                                                                       362           93                                                    Si(HSO.sub.3).sub.4                                                                       371           91                                                    Si(HS.sub.2 O.sub.7).sub.4                                                                312           94                                                    Si(HSO.sub.5).sub.4                                                                       335           95                                                    Si(HS.sub.2 O.sub.8).sub.4                                                                294           96                                                    Si(HS.sub.2 O.sub.3).sub.4                                                                341           93                                                    Si(HS.sub.2 O.sub.6).sub.4                                                                309           95                                                    Si(HS.sub.2 O.sub.5).sub.4                                                                312           94                                                    Si(HS.sub.2 O.sub.2).sub.4                                                                340           92                                                    Si(HS.sub.2 O.sub.4).sub.4                                                                318           93                                                    Si(HSO.sub.2).sub.4                                                                       390           90                                                    Pb(HSO.sub.4).sub.2                                                                       415           92                                                    Pb(HSO.sub.3).sub.2                                                                       426           91                                                    Pb(HS.sub.2 O.sub.7).sub.2                                                                386           95                                                    Pb(HSO.sub.5).sub.2                                                                       403           94                                                    Pb(HS.sub.2 O.sub.8).sub.2                                                                376           95                                                    Pb(HS.sub.2 O.sub.3).sub.2                                                                411           94                                                    Pb(HS.sub.2 O.sub.6).sub.2                                                                389           96                                                    Pb(HS.sub.2 O.sub.5).sub.2                                                                399           95                                                    Pb(HS.sub.2 O.sub.2).sub.2                                                                419           91                                                    Pb(HS.sub.2 O.sub.4).sub.2                                                                391           93                                                    ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         PbSO.sub.2 475           81                                                    CdSO.sub.4 414           79                                                    CdSO.sub.3 426           78                                                    CdS.sub.2 O.sub.7                                                                         378           81                                                    CdSO.sub.5 404           82                                                    CdS.sub.2 O.sub.8                                                                         369           84                                                    CdS.sub.2 O.sub.3                                                                         410           78                                                    CdS.sub.2 O.sub.6                                                                         398           79                                                    CdS.sub.2 O.sub.5                                                                         401           80                                                    CdS.sub.2 O.sub.2                                                                         410           78                                                    CdS.sub.2 O.sub.4                                                                         389           82                                                    CdSO.sub.2 420           76                                                    Bi.sub.2 (SO.sub.4).sub.3                                                                 364           76                                                    Bi.sub.2 (SO.sub.3).sub.3                                                                 381           75                                                    Bi.sub.2 (S.sub.2 O.sub.7).sub.3                                                          324           79                                                    Bi.sub.2 (SO.sub.5).sub.3                                                                 348           78                                                    Bi.sub.2 (S.sub.2 O.sub.8).sub.3                                                          315           81                                                    Bi.sub.2 (S.sub.2 O.sub.3).sub.3                                                          346           78                                                    Bi.sub.2 (S.sub.2 O.sub.6).sub.3                                                          329           78                                                    Bi.sub.2 (S.sub.2 O.sub.5).sub.3                                                          347           76                                                    Bi.sub.2 (S.sub.2 O.sub.2).sub.3                                                          352           75                                                    Bi.sub.2 (S.sub.2 O.sub.4).sub.3                                                          333           79                                                    Bi.sub.2 (SO.sub.2).sub.3                                                                 379           75                                                    In.sub.2 (SO.sub.4).sub.3                                                                 444           83                                                    In.sub.2 (SO.sub.3).sub.3                                                                 459           81                                                    In.sub.2 (S.sub.2 O.sub.7).sub.3                                                          398           86                                                    In.sub.2 (SO.sub.5).sub.3                                                                 421           83                                                    In.sub.2 (S.sub.2 O.sub.8).sub.3                                                          389           85                                                    Pb(HSO.sub.2).sub.2                                                                       435           91                                                    Cd(HSO.sub.4).sub.2                                                                       379           89                                                    Cd(HSO.sub.3).sub.2                                                                       398           88                                                    Cd(HS.sub.2 O.sub.7).sub.2                                                                346           92                                                    Cd(HSO.sub.5).sub.2                                                                       382           93                                                    Cd(HS.sub.2 O.sub.8).sub.2                                                                341           93                                                    Cd(HS.sub.2 O.sub.3).sub.2                                                                379           90                                                    Cd(HS.sub.2 O.sub.6).sub.2                                                                370           91                                                    Cd(HS.sub.2 O.sub.5).sub.2                                                                374           93                                                    Cd(HS.sub.2 O.sub.2).sub.2                                                                379           89                                                    Cd(HS.sub.2 O.sub.4).sub.2                                                                365           93                                                    Cd(HSO.sub.2).sub.2                                                                       391           89                                                    Bi(HSO.sub.4).sub.3                                                                       337           87                                                    Bi(HSO.sub.3).sub.3                                                                       349           86                                                    Bi(HS.sub.2 O.sub.7).sub.3                                                                298           87                                                    Bi(HSO.sub.5).sub.3                                                                       315           86                                                    Bi(HS.sub.2 O.sub.8).sub.3                                                                276           90                                                    Bi(HS.sub.2 O.sub.3).sub.3                                                                313           85                                                    Bi(HS.sub.2 O.sub.6).sub.3                                                                298           86                                                    Bi(HS.sub.2 O.sub.5).sub.3                                                                313           87                                                    Bi(HS.sub.2 O.sub.2).sub.3                                                                321           84                                                    Bi(HS.sub.2 O.sub.4).sub.3                                                                303           88                                                    Bi(HSO.sub.2).sub.3                                                                       336           86                                                    In(HSO.sub.4).sub.3                                                                       416           92                                                    In(HSO.sub.3).sub.3                                                                       420           91                                                    In(HS.sub.2 O.sub.7).sub.3                                                                367           95                                                    In(HSO.sub.5).sub.3                                                                       390           94                                                    In(HS.sub.2 O.sub.8).sub.3                                                                374           96                                                    ______________________________________                                    

                  TABLE 12                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         In.sub.2 (S.sub.2 O.sub.3).sub.3                                                          432           84                                                    In.sub.2 (S.sub.2 O.sub.6).sub.3                                                          419           85                                                    In.sub.2 (S.sub.2 O.sub.5).sub.3                                                          416           85                                                    In.sub.2 (S.sub.2 O.sub.2).sub.3                                                          432           83                                                    In.sub.2 (S.sub.2 O.sub.4).sub.3                                                          398           86                                                    In.sub.2 (SO.sub.2).sub.3                                                                 456           81                                                    ZnSO.sub.4 362           75                                                    ZnSO.sub.3 379           73                                                    ZnS.sub.2 O.sub.7                                                                         334           76                                                    ZnSO.sub.5 342           75                                                    ZnS.sub.2 O.sub.8                                                                         320           76                                                    ZnS.sub.2 O.sub.3                                                                         342           76                                                    ZnS.sub.2 O.sub.6                                                                         320           76                                                    ZnS.sub.2 O.sub.5                                                                         333           75                                                    ZnS.sub.2 O.sub.2                                                                         354           74                                                    ZnS.sub.2 O.sub.4                                                                         321           76                                                    ZnSO.sub.2 382           73                                                    MgSO.sub.4 333           81                                                    MgSO.sub.3 352           79                                                    MgS.sub.2 O.sub.7                                                                         298           84                                                    MgSO.sub.5 320           82                                                    MgS.sub.2 O.sub.8                                                                         302           83                                                    MgS.sub.2 O.sub.3                                                                         325           81                                                    MgS.sub.2 O.sub.6                                                                         300           83                                                    MgS.sub.2 O.sub.5                                                                         311           82                                                    MgS.sub.2 O.sub.2                                                                         328           82                                                    MgS.sub.2 O.sub.4                                                                         305           83                                                    MgSO.sub.2 342           79                                                    In(HS.sub.2 O.sub.3).sub.3                                                                400           95                                                    In(HS.sub.2 O.sub.6).sub.3                                                                381           95                                                    In(HS.sub.2 O.sub.5).sub.3                                                                390           95                                                    In(HS.sub.2 O.sub.2).sub.3                                                                402           91                                                    In(HS.sub.2 O.sub.4).sub.3                                                                370           95                                                    In(HSO.sub.2).sub.3                                                                       420           92                                                    Zn(HSO.sub.4).sub.2                                                                       333           85                                                    Zn(HSO.sub.3).sub.2                                                                       342           84                                                    Zn(HS.sub.2 O.sub.7).sub.2                                                                300           87                                                    Zn(HSO.sub.5).sub.2                                                                       312           86                                                    Zn(HS.sub.2 O.sub.8).sub.2                                                                294           85                                                    Zn(HS.sub.2 O.sub.3).sub.2                                                                310           85                                                    Zn(HS.sub.2 O.sub.6).sub.2                                                                300           84                                                    Zn(HS.sub.2 O.sub.5).sub.2                                                                310           86                                                    Zn(HS.sub.2 O.sub.2).sub.2                                                                325           84                                                    Zn(HS.sub.2 O.sub.4).sub.2                                                                290           86                                                    Zn(HSO.sub.2).sub.2                                                                       341           84                                                    Mg(HSO.sub.4).sub.2                                                                       312           91                                                    Mg(HSO.sub.3).sub.2                                                                       330           89                                                    Mg(HS.sub.2 O.sub.7).sub.2                                                                271           93                                                    Mg(HSO.sub.5).sub.2                                                                       294           92                                                    Mg(HS.sub.2 O.sub.8).sub.2                                                                279           93                                                    Mg(HS.sub.2 O.sub.3).sub.2                                                                293           92                                                    Mg(HS.sub.2 O.sub.6).sub.2                                                                276           94                                                    Mg(HS.sub.2 O.sub.5).sub.2                                                                288           92                                                    Mg(HS.sub.2 O.sub.2).sub.2                                                                296           93                                                    Mg(HS.sub.2 O.sub.4).sub.2                                                                276           94                                                    Mg(HSO.sub.2).sub.2                                                                       302           90                                                    ______________________________________                                    

                  TABLE 13                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Ga.sub.2 (SO.sub.4).sub.3                                                                 364           76                                                    Ga.sub.2 (SO.sub.3).sub.3                                                                 382           74                                                    Ga.sub.2 (S.sub.2 O.sub.7).sub.3                                                          321           79                                                    Ga.sub.2 (SO.sub.5).sub.3                                                                 352           75                                                    Ga.sub.2 (S.sub.2 O.sub.8).sub.3                                                          312           77                                                    Ga.sub.2 (S.sub.2 O.sub.3).sub.3                                                          352           75                                                    Ga.sub.2 (S.sub.2 O.sub.6).sub.3                                                          333           76                                                    Ga.sub.2 (S.sub.2 O.sub.5).sub.3                                                          342           75                                                    Ga.sub.2 (S.sub.2 O.sub.2).sub.3                                                          354           74                                                    Ga.sub.2 (S.sub.2 O.sub.4).sub.3                                                          326           76                                                    Ga.sub.2 (SO.sub.2).sub.3                                                                 375           73                                                    Ge(SO.sub.4).sub.2                                                                        431           78                                                    Ge(SO.sub.3).sub.2                                                                        449           75                                                    Ge(S.sub.2 O.sub.7).sub.2                                                                 395           81                                                    Ge(SO.sub.5).sub.2                                                                        423           78                                                    Ge(S.sub.2 O.sub.8).sub.2                                                                 386           81                                                    Ge(S.sub.2 O.sub.3).sub.2                                                                 425           77                                                    Ge(S.sub.2 O.sub.6).sub.2                                                                 401           80                                                    Ge(S.sub.2 O.sub.5).sub.2                                                                 408           79                                                    Ge(S.sub.2 O.sub.2).sub.2                                                                 420           79                                                    Ge(S.sub.2 O.sub.4).sub.2                                                                 390           82                                                    Ge(SO.sub.2).sub.2                                                                        435           77                                                    Cr.sub.2 (SO.sub.4).sub.3                                                                 353           81                                                    Cr.sub.2 (SO.sub.3).sub.3                                                                 369           80                                                    W(SeO.sub.4).sub.2                                                                        298           79                                                    CoSO.sub.4 352           82                                                    CoSO.sub.3 362           80                                                    NiSO.sub.4 349           81                                                    Ga(HSO.sub.4).sub.3                                                                       339           86                                                    Ga(HSO.sub.3).sub.3                                                                       352           85                                                    Ga(HS.sub.2 O.sub.7).sub.3                                                                301           88                                                    Ga(HSO.sub.5).sub.3                                                                       315           84                                                    Ga(HS.sub.2 O.sub.8).sub.3                                                                294           86                                                    Ga(HS.sub.2 O.sub.3).sub.3                                                                321           87                                                    Ga(HS.sub.2 O.sub.6).sub.3                                                                303           87                                                    Ga(HS.sub.2 O.sub.5).sub.3                                                                318           86                                                    Ga(HS.sub.2 O.sub.2).sub.3                                                                321           86                                                    Ga(HS.sub.2 O.sub.4).sub.3                                                                296           84                                                    Ga(HSO.sub.2).sub.3                                                                       348           84                                                    Ge(HSO.sub.4).sub.4                                                                       412           89                                                    Ge(HSO.sub.3).sub.4                                                                       421           86                                                    Ge(HS.sub.2 O.sub.7).sub.4                                                                370           92                                                    Ge(HSO.sub.5).sub.4                                                                       396           90                                                    Ge(HS.sub.2 O.sub.8).sub.4                                                                356           93                                                    Ge(HS.sub.2 O.sub.3).sub.4                                                                387           85                                                    Ge(HS.sub.2 O.sub.6).sub.4                                                                374           88                                                    Ge(HS.sub.2 O.sub.5).sub.4                                                                373           87                                                    Ge(HS.sub.2 O.sub.2).sub.4                                                                395           89                                                    Ge(HS.sub.2 O.sub.4).sub.4                                                                365           93                                                    Ge(HSO.sub.2).sub.4                                                                       402           89                                                    Cr(HSO.sub.4).sub.3                                                                       325           92                                                    Cr(HSO.sub.3).sub.3                                                                       341           90                                                    W(HSO.sub.4).sub.4                                                                        275           89                                                    Co(HSO.sub.4).sub.2                                                                       321           92                                                    Co(HSO.sub.3).sub.2                                                                       329           90                                                    Ni(HSO.sub.4).sub.2                                                                       319           90                                                    ______________________________________                                    

                  TABLE 14                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         NiSO.sub.3  354          79                                                    CuSO.sub.4  326          82                                                    CuSO.sub.3  340          80                                                    Ti.sub.2 (SO.sub.4).sub.3                                                                  315          83                                                    Mo.sub.2 (SO.sub.4).sub.3                                                                  324          84                                                    VSO.sub.4   306          83                                                    MnSO.sub.4  345          82                                                    MnSO.sub.3  356          80                                                    FeSO.sub.4  354          81                                                    FeSO.sub.3  362          78                                                    Nb.sub.2 (SO.sub.4).sub.5                                                                  257          82                                                    CaSO.sub.4  398          78                                                    CaSO.sub.3  405          76                                                    SrSO.sub.4  398          78                                                    SrSO.sub.3  405          76                                                    BaSO.sub.4  375          79                                                    BaSO.sub.3  386          78                                                    Ni(HSO.sub.3).sub.2                                                                        326          88                                                    Cu(HSO.sub.4).sub.2                                                                        301          93                                                    Cu(HSO.sub.3).sub.2                                                                        319          91                                                    Ti(HSO.sub.4).sub.3                                                                        284          90                                                    Mo(HSO.sub.4).sub.3                                                                        299          92                                                    V(HSO.sub.4).sub.2                                                                         274          92                                                    Mn(HSO.sub.4).sub.2                                                                        315          93                                                    Mn(HSO.sub.3).sub.2                                                                        320          90                                                    Fe(HSO.sub.4).sub.2                                                                        327          91                                                    Fe(HSO.sub.3).sub.2                                                                        333          89                                                    Nb(HSO.sub.4).sub.5                                                                        229          90                                                    Ca(HSO.sub.4).sub.2                                                                        375          87                                                    Ca(HSO.sub.3).sub.2                                                                        381          85                                                    Sr(HSO.sub.4).sub.2                                                                        375          87                                                    Sr(HSO.sub.3).sub.2                                                                        381          85                                                    Ba(HSO.sub.4).sub.2                                                                        352          87                                                    Ba(HSO.sub.3).sub.2                                                                        360          86                                                    ______________________________________                                    

                  TABLE 15                                                         ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Mg.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               503          84                                                  Sr.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               503          84                                                  Ca.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               503          84                                                  Zn.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               500          85                                                  Ni.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               495          84                                                  Fe.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               492          86                                                  Co.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               489          87                                                  Mn.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               482          86                                                  Cu.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               485          85                                                  Mo.sub.0.1 Sn.sub.0.9 SO.sub.4                                                               476          84                                                  V.sub.0.1 Sn.sub.0.9 SO.sub.4                                                                473          86                                                  W.sub.0.1 Sn.sub.0.8 SO.sub.4                                                                459          83                                                  Cr.sub.0.2 Sn.sub.0.7 SO.sub.4                                                               476          84                                                  Mo.sub.0.2 Sn.sub.0.7 SO.sub.4                                                               476          85                                                  Mg.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               420          86                                                  Sr.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               420          86                                                  Ca.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               420          86                                                  Zn.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               421          87                                                  Ni.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               415          86                                                  Fe.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               410          87                                                  Co.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               416          88                                                  Mn.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               408          86                                                  Cu.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               406          87                                                  Mo.sub.0.1 Pb.sub.0.9 SO.sub.4                                                               398          85                                                  V.sub.0.1 Pb.sub.0.9 SO.sub.4                                                                387          85                                                  W.sub.0.1 Pb.sub.0.8 SO.sub.4                                                                376          85                                                  Cr.sub.0.2 Pb.sub.0.7 SO.sub.4                                                               387          84                                                  Mo.sub.0.2 Pb.sub.0.7 SO.sub.4                                                               389          85                                                  Mg.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      481          94                                                  Sr.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      481          94                                                  Ca.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      481          94                                                  Zn.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      479          95                                                  Ni.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      470          95                                                  Fe.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      476          95                                                  Co.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      469          94                                                  Mn.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      465          96                                                  Cu.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      462          94                                                  Mo.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                      459          95                                                  V.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2                                                       451          95                                                  W.sub.0.1 Sn.sub.0.8 (HSO.sub.4).sub.2                                                       432          94                                                  Cr.sub.0.2 Sn.sub.0.7 (HSO.sub.4).sub.2                                                      455          94                                                  Mo.sub.0.2 Sn.sub.0.7 (HSO.sub.4).sub.2                                                      452          95                                                  Mg.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      394          95                                                  Sr.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      394          95                                                  Ca.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      394          95                                                  Zn.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      394          94                                                  Ni.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      384          97                                                  Fe.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      381          95                                                  Co.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      384          96                                                  Mn.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      381          95                                                  Cu.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      386          96                                                  Mo.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                      370          95                                                  V.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2                                                       368          94                                                  W.sub.0.1 Pb.sub.0.5 (HSO.sub.4).sub.2                                                       359          95                                                  Cr.sub.0.2 Pb.sub.0.7 (HSO.sub.4).sub.2                                                      364          94                                                  Mo.sub.0.2 Pb.sub.0.7 (HSO.sub.4).sub.2                                                      368          94                                                  ______________________________________                                    

                  TABLE 16                                                         ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         (Mg.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3                                               410          85                                                  (Zn.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3                                               406          86                                                  (Ni.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3                                               398          86                                                  (Co.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3                                               333          80                                                  (Fe.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3                                               325          82                                                  (Mn.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3                                               330          80                                                  Sn(SO.sub.4).sub.0.5 (HSO.sub.4)                                                             498          90                                                  Pb(SO.sub.4).sub.0.5 (HSO.sub.4)                                                             425          90                                                  In.sub.2 (SO.sub.4).sub.2.5 (HSO.sub.4)                                                      425          90                                                  Bi.sub.2 (SO.sub.4).sub.2.5 (HSO.sub.4)                                                      343          84                                                  Co.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3                                                      379          94                                                  Fe.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3                                                      370          95                                                  Mn.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3                                                      368          95                                                  Mg.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3                                                      298          90                                                  Zn.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3                                                      289          89                                                  Ni.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3                                                      295          91                                                  Sn(SO.sub.4).sub.0.9 (HSO.sub.4).sub.0.2                                                     519          86                                                  Pb(SO.sub.4).sub.0.9 (HSO.sub.4).sub.0.2                                                     438          87                                                  In.sub.2 (SO.sub.4).sub.2.9 (HSO.sub.4).sub.0.2                                              438          86                                                  Bi.sub.2 (SO.sub.4).sub.2.9 (HSO.sub.4).sub.0.2                                              350          80                                                  ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 4.

The batteries using the metal or semi-metal sulfate, sulfite, disulfate, peroxomonosulfate, peroxodisulfate, thiosulfate, disulfite, thiosulfite, hydrogensulfate, thionate, or sulfoxylate of Example 4 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogensulfates has remarkably improved the cycle characteristics.

EXAMPLE 5

The electrode characteristics of various salts of oxo-acids of selenium specified in Tables 17 through 20 and used as the anode active material were evaluated in Example 5.

Tables 17 through 20 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 17                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (SeO.sub.4).sub.3                                                                 362          83                                                    Al.sub.2 (SeO.sub.3).sub.3                                                                 387          80                                                    Sn(SeO.sub.4).sub.2                                                                        462          84                                                    Sn(SeO.sub.3).sub.2                                                                        483          81                                                    SnSeO.sub.4 512          83                                                    SnSeO.sub.3 521          80                                                    Sn.sub.2 SeO.sub.5                                                                         534          79                                                    Si(SeO.sub.4).sub.2                                                                        364          84                                                    Si(SeO.sub.3).sub.2                                                                        379          80                                                    PbSeO.sub.4 432          85                                                    PbSeO.sub.3 445          82                                                    Pb.sub.2 SeO.sub.5                                                                         498          80                                                    CdSeO.sub.4 386          80                                                    CdSeO.sub.3 399          78                                                    Bi.sub.2 (SeO.sub.4).sub.3                                                                 339          77                                                    Bi.sub.2 (SeO.sub.3).sub.3                                                                 349          72                                                    In.sub.2 (SeO.sub.4).sub.3                                                                 421          85                                                    In.sub.2 (SeO.sub.3).sub.3                                                                 438          83                                                    ZnSeO.sub.4 339          74                                                    ZnSeO.sub.3 348          70                                                    MgSeO.sub.4 310          82                                                    MgSeO.sub.3 321          79                                                    Ga.sub.2 (SeO.sub.4).sub.3                                                                 339          75                                                    Ga.sub.2 (SeO.sub.3).sub.3                                                                 349          73                                                    Ge(SeO.sub.4).sub.2                                                                        405          77                                                    Ge(SeO.sub.3).sub.2                                                                        420          72                                                    Al(HSeO.sub.4).sub.3                                                                       341          92                                                    Al(HSeO.sub.3).sub.3                                                                       367          89                                                    Sn(HSeO.sub.4).sub.4                                                                       442          92                                                    Sn(HSeO.sub.3).sub.4                                                                       462          93                                                    Sn(HSeO.sub.4).sub.2                                                                       489          94                                                    Sn(HSeO.sub.3).sub.2                                                                       501          90                                                    SnSeO.sub.5 508          84                                                    Si(HSeO.sub.4).sub.4                                                                       342          92                                                    Si(HSeO.sub.3).sub.4                                                                       347          90                                                    Pb(HSeO.sub.4).sub.2                                                                       412          93                                                    Pb(HSeO.sub.3).sub.2                                                                       421          92                                                    PbSeO.sub.5 425          85                                                    Cd(HSeO.sub.4).sub.2                                                                       364          90                                                    Cd(HSeO.sub.3).sub.2                                                                       374          88                                                    Bi(HSeO.sub.4).sub.3                                                                       314          89                                                    Bi(HSeO.sub.3).sub.3                                                                       321          86                                                    In(HSeO.sub.4).sub.3                                                                       397          94                                                    In(HSeO.sub.3).sub.3                                                                       409          93                                                    Zn(HSeO.sub.4).sub.2                                                                       315          85                                                    Zn(HSeO.sub.3).sub.2                                                                       320          83                                                    Mg(HSeO.sub.4).sub.2                                                                       289          92                                                    Mg(HSeO.sub.3).sub.2                                                                       301          87                                                    Ga(HSeO.sub.4).sub.3                                                                       314          86                                                    Ga(HSeO.sub.3).sub.3                                                                       324          84                                                    Ge(HSeO.sub.4).sub.4                                                                       385          86                                                    Ge(HSeO.sub.3).sub.4                                                                       396          83                                                    ______________________________________                                    

                  TABLE 18                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Cr.sub.2 (SeO.sub.4).sub.3                                                                 321          75                                                    Cr.sub.2 (SeO.sub.3).sub.3                                                                 331          76                                                    W(SeO.sub.4).sub.2                                                                         257          72                                                    CoSeO.sub.4 286          73                                                    CoSeO.sub.3 297          76                                                    NiSeO.sub.4 286          76                                                    NiSeO.sub.3 299          76                                                    CuSeO.sub.4 287          73                                                    CuSeO.sub.3 289          74                                                    Ti.sub.2 (SeO.sub.4).sub.3                                                                 253          77                                                    Mo.sub.2 (SeO.sub.4).sub.3                                                                 223          73                                                    VSeO.sub.4  282          79                                                    MnSeO.sub.4 265          73                                                    MnSeO.sub.3 276          75                                                    FeSeO.sub.4 282          74                                                    FeSeO.sub.3 293          75                                                    Nb.sub.2 (SeO.sub.4).sub.5                                                                 215          75                                                    CaSeO.sub.4 321          74                                                    CaSeO.sub.3 334          76                                                    SrSeO.sub.3 334          76                                                    BaSeO.sub.4 345          73                                                    BaSeO.sub.3 353          74                                                    Sb.sub.2 (SeO.sub.4).sub.3                                                                 364          72                                                    Ir.sub.2 (SeO.sub.4).sub.3                                                                 345          73                                                    Cr(HSeO.sub.4).sub.3                                                                       305          84                                                    Cr(HSeO.sub.3).sub.3                                                                       314          86                                                    W(HSeO.sub.4).sub.4                                                                        234          83                                                    Co(HSeO.sub.4).sub.2                                                                       261          82                                                    Co(HSeO.sub.3).sub.2                                                                       271          85                                                    Ni(HSeO.sub.4).sub.2                                                                       264          84                                                    Ni(HSeO.sub.3).sub.2                                                                       274          85                                                    Cu(HSeO.sub.4).sub.2                                                                       264          84                                                    Cu(HSeO.sub.3).sub.2                                                                       259          84                                                    Ti(HSeO.sub.4).sub.3                                                                       230          86                                                    Mo(HSeO.sub.4).sub.3                                                                       201          84                                                    V(HSeO.sub.4).sub.2                                                                        261          89                                                    Mn(HSeO.sub.4).sub.2                                                                       241          82                                                    Mn(HSeO.sub.3).sub.2                                                                       251          84                                                    Fe(HSeO.sub.4).sub.2                                                                       260          86                                                    Fe(HSeO.sub.3).sub.2                                                                       271          85                                                    Nb(HSeO.sub.4).sub.5                                                                       195          84                                                    Ca(HSeO.sub.4).sub.2                                                                       301          82                                                    Ca(HSeO.sub.3).sub.2                                                                       309          85                                                    Sr(HSeO.sub.3).sub.2                                                                       309          85                                                    Ba(HSeO.sub.4).sub.2                                                                       314          84                                                    Ba(HSeO.sub.3).sub.2                                                                       321          83                                                    Sb(HSeO.sub.4).sub.3                                                                       335          86                                                    Ir(HSeO.sub.4).sub.3                                                                       315          85                                                    ______________________________________                                    

                  TABLE 19                                                         ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Mg.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              486          85                                                  Zn.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              484          86                                                  Ni.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              472          85                                                  Fe.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              471          86                                                  Co.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              476          87                                                  Mn.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              483          84                                                  Cu.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              475          85                                                  Mo.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              465          86                                                  V.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                               459          88                                                  W.sub.0.1 Sn.sub.0.8 SeO.sub.4                                                               443          88                                                  Cr.sub.0.2 Sn.sub.0.7 SeO.sub.4                                                              433          86                                                  Ca.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              492          85                                                  Sr.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              492          85                                                  Ba.sub.0.1 Sn.sub.0.9 SeO.sub.4                                                              475          86                                                  Mg.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              415          85                                                  Zn.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              409          86                                                  Ni.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              414          87                                                  Fe.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              401          88                                                  Co.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              405          86                                                  Mn.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              403          84                                                  Cu.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              402          85                                                  Mo.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              394          85                                                  V.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                               396          84                                                  W.sub.0.1 Pb.sub.0.8 SeO.sub.4                                                               379          86                                                  Cr.sub.0.2 Pb.sub.0.7 SeO.sub.4                                                              368          85                                                  Ca.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              408          85                                                  Sr.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              408          85                                                  Ba.sub.0.1 Pb.sub.0.9 SeO.sub.4                                                              381          86                                                  Mg.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     453          94                                                  Zn.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     461          96                                                  Ni.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     453          95                                                  Fe.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     449          94                                                  Co.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     448          95                                                  Mn.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     457          92                                                  Cu.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     453          94                                                  Mo.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     441          95                                                  V.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                      432          97                                                  W.sub.0.1 Sn.sub.0.8 (HSeO.sub.4).sub.2                                                      420          96                                                  Cr.sub.0.2 Sn.sub.0.7 (HSeO.sub.4).sub.2                                                     416          95                                                  Ca.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     470          95                                                  Sr.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     470          95                                                  Ba.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2                                                     448          94                                                  Mg.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     385          94                                                  Zn.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     389          95                                                  Ni.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     391          96                                                  Fe.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     371          98                                                  Co.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     379          95                                                  Mn.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     371          95                                                  Cu.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     376          96                                                  Mo.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     370          94                                                  V.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                      369          95                                                  W.sub.0.1 Pb.sub.0.8 (HSeO.sub.4).sub.2                                                      349          97                                                  Cr.sub.0.2 Pb.sub.0.7 (HSeO.sub.4).sub.2                                                     333          96                                                  Ca.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     379          94                                                  Sr.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     379          94                                                  Ba.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2                                                     353          96                                                  ______________________________________                                    

                  TABLE 20                                                         ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         (Mg.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              398          86                                                  (Zn.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              387          87                                                  (Ni.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              379          86                                                  (Co.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              318          80                                                  (Fe.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              310          82                                                  (Mn.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3                                              320          82                                                  Co.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3                                                     374          95                                                  Fe.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3                                                     361          98                                                  Mn.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3                                                     348          96                                                  Mg.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.3                                                     279          91                                                  Zn.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.3                                                     284          92                                                  Ni.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.3                                                     298          93                                                  ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 5.

The batteries using the metal or semi-metal selenate, selenite, hydrogenselenate, or hydrogenselenite of Example 5 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogenselenates and hydrogenselenites has remarkably improved the cycle characteristics.

EXAMPLE 6

The electrode characteristics of various salts of oxo-acids of tellurium specified in Tables 21 through 23 and used as the anode active material were evaluated in Example 6.

Tables 21 through 23 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 21                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (TeO.sub.4).sub.3                                                                 346          82                                                    SnTeO.sub.4 426          84                                                    SnTe.sub.3 O.sub.8                                                                         385          87                                                    Sn.sub.3 TeO.sub.6                                                                         489          85                                                    Si(TeO.sub.4).sub.2                                                                        337          83                                                    PbTeO.sub.4 405          84                                                    PbTe.sub.3 O.sub.8                                                                         352          85                                                    Pb.sub.3 TeO.sub.6                                                                         453          82                                                    CdTeO.sub.4 354          79                                                    Bi.sub.2 (TeO.sub.4).sub.3                                                                 314          79                                                    Bi.sub.2 TeO.sub.6                                                                         345          77                                                    In.sub.2 (TeO.sub.4).sub.3                                                                 384          82                                                    In.sub.2 TeO.sub.6                                                                         405          80                                                    Sb.sub.2 TeO.sub.6                                                                         384          78                                                    Ir.sub.2 TeO.sub.6                                                                         351          78                                                    ZnTeO.sub.4 302          75                                                    MgTeO.sub.4 289          81                                                    Ga.sub.2 TeO.sub.6                                                                         314          74                                                    Ge(TeO.sub.4).sub.2                                                                        370          75                                                    Ti.sub.2 TeO.sub.6                                                                         221          78                                                    Cr.sub.2 TeO.sub.6                                                                         287          74                                                    NiTeO.sub.4 253          76                                                    FeTeO.sub.4 254          75                                                    MnTeO.sub.4 247          74                                                    CoTeO.sub.4 253          75                                                    VTeO.sub.4  241          76                                                    CuTeO.sub.4 251          75                                                    Al(HTeO.sub.4).sub.3                                                                       319          89                                                    Sn(HTeO.sub.4).sub.2                                                                       397          90                                                    SnH.sub.4 TeO.sub.6                                                                        359          95                                                    Sn.sub.2 H.sub.2 TeO.sub.6                                                                 459          94                                                    Si(HTeO.sub.4).sub.4                                                                       307          93                                                    Pb(HTeO.sub.4).sub.2                                                                       372          92                                                    PbH.sub.4 TeO.sub.6                                                                        321          94                                                    Pb.sub.2 H.sub.2 TeO.sub.6                                                                 426          93                                                    Cd(HTeO.sub.4).sub.2                                                                       320          90                                                    Bi(HTeO.sub.4).sub.3                                                                       284          87                                                    BiH.sub.3 TeO.sub.6                                                                        314          87                                                    In(HTeO.sub.4).sub.3                                                                       359          89                                                    InH.sub.3 TeO.sub.6                                                                        374          90                                                    SbH.sub.3 TeO.sub.6                                                                        352          89                                                    IrH.sub.3 TeO.sub.6                                                                        321          88                                                    Zn(HTeO.sub.4).sub.2                                                                       275          86                                                    Mg(HSeO.sub.4).sub.2                                                                       264          89                                                    GaH.sub.3 TeO.sub.6                                                                        275          86                                                    Ge(HTeO.sub.4).sub.4                                                                       342          86                                                    TiH.sub.3 TeO.sub.6                                                                        198          87                                                    CrH.sub.3 TeO.sub.6                                                                        255          86                                                    Ni(HTeO.sub.4).sub.2                                                                       234          87                                                    Fe(HSeO.sub.4).sub.2                                                                       229          86                                                    Mn(HTeO.sub.4).sub.2                                                                       219          85                                                    Co(HSeO.sub.4).sub.2                                                                       218          85                                                    V(HTeO.sub.4).sub.2                                                                        214          87                                                    Cu(HTeO.sub.4).sub.2                                                                       216          85                                                    ______________________________________                                    

                  TABLE 22                                                         ______________________________________                                                                   Capacity                                                          Discharge capacity                                                                          maintenance rate                                     Salt         (mAh/g)      (%)                                                  ______________________________________                                         MoTeO.sub.4  234          73                                                   W(TeO.sub.4).sub.2                                                                          215          73                                                   CaTeO.sub.4  315          74                                                   SrTeO.sub.4  315          74                                                   BaTeO.sub.4  305          75                                                   Mg.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             402          86                                                   Cag.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                            402          86                                                   Srg.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                            402          86                                                   Zn.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             405          85                                                   Ni.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             400          86                                                   Fe.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             398          87                                                   Co.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             396          86                                                   Mn.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             389          85                                                   Cu.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             390          85                                                   Mo.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                             379          87                                                   V.sub.0.1 Sn.sub.0.9 TeO.sub.4                                                              378          88                                                   W.sub.0.1 Sn.sub.0.8 TeO.sub.4                                                              369          85                                                   Cr.sub.0.2 Sn.sub.0.7 TeO.sub.4                                                             374          86                                                   Mg.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             375          86                                                   Ca.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             375          86                                                   Sr.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             375          86                                                   Zn.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             379          85                                                   Ni.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             370          87                                                   Fe.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             367          88                                                   Co.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             368          87                                                   Mn.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             364          86                                                   Cu.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             362          87                                                   Mo.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                             354          87                                                   V.sub.0.1 Pb.sub.0.9 TeO.sub.4                                                              352          86                                                   W.sub.0.1 Pb.sub.0.8 TeO.sub.4                                                              341          85                                                   Mo(HTeO.sub.4).sub.2                                                                        215          81                                                   W(HTeO.sub.4).sub.4                                                                         185          82                                                   Ca(HTeO.sub.4).sub.2                                                                        289          84                                                   Sr(HTeO.sub.4).sub.2                                                                        289          84                                                   Ba(HTeO.sub.4).sub.2                                                                        279          83                                                   Mg.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    375          95                                                   Ca.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    375          95                                                   Sr.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    375          95                                                   Zn.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    379          94                                                   Ni.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    374          95                                                   Fe.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    370          96                                                   Co.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    375          95                                                   Mn.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    369          94                                                   Cu.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    371          94                                                   Mo.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                    352          95                                                   V.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2                                                     349          97                                                   W.sub.0.1 Sn.sub.0.8 (HTeO.sub.4).sub.2                                                     342          95                                                   Cr.sub.0.2 Sn.sub.0.7 (HTeO.sub.4).sub.2                                                    344          94                                                   Mg.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    335          95                                                   Ca.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    335          95                                                   Sr.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    335          95                                                   Zn.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    339          94                                                   Ni.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    348          95                                                   Fe.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    332          96                                                   Co.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    321          95                                                   Mn.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    322          94                                                   Cu.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    337          95                                                   Mo.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                    326          94                                                   V.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2                                                     322          95                                                   W.sub.0.1 Pb.sub.0.8 (HTeO.sub.4).sub.2                                                     320          96                                                   ______________________________________                                    

                  TABLE 23                                                         ______________________________________                                                                   Capacity                                                          Discharge capacity                                                                          maintenance rate                                     Salt         (mAh/g)      (%)                                                  ______________________________________                                         Cr.sub.0.2 Pb.sub.0.7 TeO.sub.4                                                             361          84                                                   (Mg.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6                                                     374          82                                                   (Zn.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6                                                     370          83                                                   (Fe.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6                                                     364          84                                                   (Mg.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6                                                     315          79                                                   (Zn.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6                                                     318          80                                                   (Fe.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6                                                     308          81                                                   Cr.sub.0.2 Pb.sub.0.7 (HTeO.sub.4).sub.2                                                    337          93                                                   Co.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6                                                     351          93                                                   Ni.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6                                                     341          92                                                   Mn.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6                                                     338          92                                                   Co.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.6                                                     287          88                                                   Ni.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.6                                                     286          90                                                   Mn.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.6                                                     279          90                                                   ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 6.

The batteries using the metal or semi-metal tellurate or hydrogentellurate of Example 6 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogentellurates has remarkably improved the cycle characteristics.

EXAMPLE 7

The electrode characteristics of various metal and semi-metal hydrogenphosphates, phosphinates, and phosphonates specified in Tables 24 through 27 and used as the anode active material were evaluated in Example 7.

Tables 24 through 27 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 24                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al(PH.sub.2 O.sub.2).sub.3                                                                 366          83                                                    Al.sub.2 (PHO.sub.3).sub.3                                                                 353          84                                                    Al.sub.2 (HPO.sub.4).sub.3                                                                 348          85                                                    Al(H.sub.2 PO.sub.4).sub.3                                                                 315          87                                                    Sn(PH.sub.2 O.sub.2).sub.4                                                                 412          88                                                    Sn(PHO.sub.3).sub.2                                                                        455          89                                                    Sn(HPO.sub.4).sub.2                                                                        452          88                                                    Sn(H.sub.2 PO.sub.4).sub.4                                                                 384          89                                                    Sn(PH.sub.2 O.sub.2).sub.2                                                                 452          82                                                    SnPHO.sub.3 486          92                                                    SnHPO.sub.4 485          95                                                    Sn(H.sub.2 PO.sub.4).sub.2                                                                 402          86                                                    Si(PH.sub.2 O.sub.2).sub.4                                                                 304          85                                                    Si(PHO.sub.3).sub.2                                                                        332          86                                                    Bi(PH.sub.2 O.sub.2).sub.3                                                                 333          82                                                    Bi.sub.2 (PHO.sub.3).sub.3                                                                 345          83                                                    Bi.sub.2 (HPO.sub.4).sub.3                                                                 340          83                                                    Bi(H.sub.2 PO.sub.4).sub.3                                                                 324          85                                                    In(PH.sub.2 O.sub.2).sub.3                                                                 365          82                                                    In.sub.2 (PHO.sub.3).sub.3                                                                 380          81                                                    In.sub.2 (HPO.sub.4).sub.3                                                                 377          83                                                    In(H.sub.2 PO.sub.4).sub.3                                                                 333          86                                                    Zn(PH.sub.2 O.sub.2).sub.2                                                                 298          83                                                    ZnPHO.sub.3 298          83                                                    ZnHPO.sub.4 295          83                                                    Zn(H.sub.2 PO.sub.4).sub.2                                                                 264          84                                                    Mg(PH.sub.2 O.sub.2).sub.2                                                                 281          84                                                    MgPHO.sub.3 288          83                                                    ______________________________________                                    

                  TABLE 25                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Si(HPO.sub.4).sub.2                                                                        322          87                                                    Si(H.sub.2 PO.sub.4).sub.4                                                                 285          88                                                    Pb(PH.sub.2 O.sub.2).sub.2                                                                 420          85                                                    PbPHO.sub.3 425          85                                                    PbHPO.sub.4 418          89                                                    Pb(H.sub.2 PO.sub.4).sub.2                                                                 405          90                                                    Cd(PH.sub.2 O.sub.2).sub.2                                                                 380          82                                                    CdPHO.sub.3 385          83                                                    CdHPO.sub.4 384          83                                                    Cd(H.sub.2 PO.sub.4).sub.2                                                                 375          86                                                    Sb.sub.2 (HPO.sub.4).sub.3                                                                 321          82                                                    Ti.sub.2 (HPO.sub.4).sub.3                                                                 275          84                                                    V.sub.2 (HPO.sub.4).sub.3                                                                  250          85                                                    Cr.sub.2 (HPO.sub.4).sub.3                                                                 284          84                                                    Mn.sub.2 (HPO.sub.4).sub.3                                                                 275          85                                                    MgHPO.sub.4 286          84                                                    Mg(H.sub.2 PO.sub.4).sub.2                                                                 267          87                                                    Ga(PH.sub.2 O.sub.2).sub.3                                                                 321          82                                                    Ga.sub.2 (PHO.sub.3).sub.3                                                                 335          83                                                    Ga.sub.2 (HPO.sub.4).sub.3                                                                 325          84                                                    Ga(H.sub.2 PO.sub.4).sub.3                                                                 305          86                                                    Ge(PH.sub.2 O.sub.2).sub.4                                                                 367          83                                                    Ge(PHO.sub.3).sub.2                                                                        382          84                                                    Ge(HPO.sub.4).sub.2                                                                        375          87                                                    Ge(H.sub.2 PO.sub.4).sub.4                                                                 342          89                                                    Fe.sub.2 (HPO.sub.4).sub.3                                                                 264          85                                                    CoHPO.sub.4 264          84                                                    NiHPO.sub.4 261          84                                                    CuHPO.sub.4 275          85                                                    ______________________________________                                    

                  TABLE 26                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         SrHPO.sub.4 332          85                                                    Ca.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            451          88                                                    Sr.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            451          88                                                    Ba.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            432          89                                                    Zn.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            437          92                                                    Fe.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            441          91                                                    Ni.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            438          92                                                    Co.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            442          92                                                    Mn.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            429          90                                                    Ti.sub.0.2 Sn.sub.0.7 HPO.sub.4                                                            415          91                                                    Cu.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                            429          92                                                    Cr.sub.0.2 Sn.sub.0.7 HPO.sub.4                                                            418          93                                                    V.sub.0.2 Sn.sub.0.8 HPO.sub.4                                                             404          91                                                    W.sub.0.1 Sn.sub.0.8 HPO.sub.4                                                             406          90                                                    BaHPO.sub.4 312          86                                                    Ca.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            372          90                                                    Sr.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            372          90                                                    Ba.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            359          91                                                    Zn.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            382          93                                                    Fe.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            374          94                                                    Ni.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            368          93                                                    Co.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            376          92                                                    Mn.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            374          93                                                    Ti.sub.0.2 Pb.sub.0.7 HPO.sub.4                                                            369          94                                                    Cu.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                            371          93                                                    Cr.sub.0.2 Pb.sub.0.7 HPO.sub.4                                                            368          95                                                    V.sub.0.2 Pb.sub.0.8 HPO.sub.4                                                             365          93                                                    W.sub.0.1 Pb.sub.0.8 HPO.sub.4                                                             345          93                                                    ______________________________________                                    

                  TABLE 27                                                         ______________________________________                                                                    Capacity                                                          Discharge capacity                                                                          maintenance rate                                    Salt          (mAh/g)      (%)                                                 ______________________________________                                         Sn.sub.2 (P.sub.2 O.sub.7).sub.0.9 (HPO.sub.4).sub.0.2                                       495          82                                                  Sn.sub.2 (P.sub.2 O.sub.7).sub.0.8 (HPO.sub.4).sub.0.4                                       490          88                                                  Pb.sub.2 (P.sub.2 O.sub.7).sub.0.9 (HPO.sub.4).sub.0.2                                       425          80                                                  Pb.sub.2 (P.sub.2 O.sub.7).sub.0.8 (HPO.sub.4).sub.0.4                                       422          82                                                  ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 7.

The batteries using the metal or semi-metal hydrogenphosphate, phosphinate, or phosphonate of Example 7 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 8

The electrode characteristics of various metal and semi-metal cyanides, cyanates, and thiocyanates specified in Tables 28 through 30 and used as the anode active material were evaluated in Example 8.

Tables 28 through 30 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 28                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al(CN).sub.3                                                                               382          76                                                    Al(SCN).sub.3                                                                              286          82                                                    Al(ONC).sub.3                                                                              364          80                                                    Sn(CN).sub.4                                                                               529          85                                                    Sn(SCN).sub.4                                                                              326          92                                                    Sn(ONC).sub.4                                                                              436          90                                                    Sn(CN).sub.2                                                                               537          82                                                    Sn(SCN).sub.2                                                                              487          95                                                    Sn(ONC).sub.2                                                                              506          93                                                    Si(CN).sub.4                                                                               315          76                                                    Si(SCN).sub.4                                                                              292          82                                                    Si(ONC).sub.4                                                                              310          79                                                    Pb(CN).sub.2                                                                               454          82                                                    Pb(SCN).sub.2                                                                              346          88                                                    Pb(ONC).sub.2                                                                              386          87                                                    Cd(CN).sub.2                                                                               372          75                                                    Cd(SCN).sub.2                                                                              315          79                                                    Cd(ONC).sub.2                                                                              340          79                                                    Bi(CN).sub.3                                                                               324          75                                                    Bi(SCN).sub.3                                                                              286          86                                                    Bi(ONC).sub.3                                                                              316          80                                                    In(CN).sub.3                                                                               412          82                                                    In(SCN).sub.3                                                                              375          89                                                    In(ONC).sub.3                                                                              369          86                                                    Zn(CN).sub.2                                                                               315          76                                                    Zn(SCN).sub.2                                                                              285          83                                                    Zn(ONC).sub.2                                                                              310          79                                                    Ga(CN).sub.3                                                                               348          74                                                    Ga(SCN).sub.3                                                                              302          79                                                    Ga(ONC).sub.3                                                                              326          76                                                    Ge(CN).sub.4                                                                               390          78                                                    Ge(SCN).sub.4                                                                              352          86                                                    Ge(ONC).sub.4                                                                              389          82                                                    Mg(CN).sub.2                                                                               320          79                                                    Mg(SCN).sub.2                                                                              289          89                                                    Mg(ONC).sub.2                                                                              341          85                                                    ______________________________________                                    

                  TABLE 29                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Ti(CN).sub.3                                                                               265          75                                                    Ti(SCN).sub.3                                                                              251          77                                                    Ti(ONC).sub.3                                                                              263          75                                                    V(CN).sub.2 275          81                                                    V(SCN).sub.2                                                                               245          82                                                    V(ONC).sub.2                                                                               263          80                                                    Mn(CN).sub.2                                                                               278          82                                                    Mn(SCN).sub.2                                                                              261          87                                                    Mn(ONC).sub.2                                                                              275          85                                                    Sb(CN).sub.3                                                                               315          76                                                    Sb(SCN).sub.3                                                                              281          80                                                    Sb(ONC).sub.3                                                                              298          78                                                    Cr(CN).sub.3                                                                               301          82                                                    Cr(SCN).sub.3                                                                              275          84                                                    Cr(ONC).sub.3                                                                              280          83                                                    Fe(CN).sub.2                                                                               269          75                                                    Fe(SCN).sub.2                                                                              245          79                                                    Fe(ONC).sub.2                                                                              257          79                                                    W(CN).sub.4 215          81                                                    W(SCN).sub.4                                                                               201          82                                                    W(ONC).sub.4                                                                               210          81                                                    Co(CN).sub.2                                                                               269          78                                                    Co(SCN).sub.2                                                                              245          84                                                    Co(ONC).sub.2                                                                              253          80                                                    Ni(CN).sub.2                                                                               275          82                                                    Ni(SCN).sub.2                                                                              257          86                                                    Ni(ONC).sub.2                                                                              261          81                                                    Cu(CN).sub.2                                                                               251          77                                                    Cu(SCN).sub.2                                                                              235          80                                                    Cu(ONC).sub.2                                                                              246          78                                                    Mo(CN).sub.3                                                                               235          77                                                    Mo(SCN).sub.3                                                                              211          79                                                    Mo(ONC).sub.3                                                                              225          77                                                    Ca(CN).sub.2                                                                               325          78                                                    Ca(SCN).sub.2                                                                              314          84                                                    Ca(ONC).sub.2                                                                              322          80                                                    Ba(CN).sub.2                                                                               333          79                                                    Ba(SCN).sub.2                                                                              301          87                                                    Ba(ONC).sub.2                                                                              311          81                                                    Nb(CN).sub.2                                                                               222          82                                                    Nb(SCN).sub.2                                                                              201          83                                                    Nb(ONC).sub.2                                                                              216          81                                                    Sr(SCN).sub.2                                                                              314          84                                                    Sr(ONC).sub.2                                                                              322          80                                                    ______________________________________                                    

                  TABLE 30                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         ZnSn(CN).sub.4                                                                             402          87                                                    MgSn(SCN).sub.4                                                                            382          92                                                    CaSn(SCN).sub.4                                                                            382          92                                                    Sr(SCN).sub.4                                                                              382          92                                                    FeSn(ONC).sub.4                                                                            376          91                                                    NiSn(CN).sub.4                                                                             398          88                                                    CoSn(SCN).sub.4                                                                            375          93                                                    MnSn(ONC).sub.4                                                                            390          92                                                    TiSn(CN).sub.5                                                                             385          87                                                    CuSn(SCN).sub.4                                                                            360          93                                                    NiPb(CN).sub.4                                                                             382          83                                                    CoPb(SCN).sub.4                                                                            362          85                                                    MnPb(ONC).sub.4                                                                            375          84                                                    ZnPb(CN).sub.4                                                                             395          84                                                    MgPb(SCN).sub.4                                                                            376          89                                                    CaPb(SCN).sub.4                                                                            376          89                                                    SrPb(SCN).sub.4                                                                            376          89                                                    FePb(ONC).sub.4                                                                            375          89                                                    TiPb(CN).sub.5                                                                             376          84                                                    CuPb(SCN).sub.4                                                                            326          89                                                    CuIn(CN).sub.5                                                                             355          84                                                    FeIn(SCN).sub.5                                                                            335          91                                                    CoIn(ONC).sub.5                                                                            345          88                                                    MgIn(CN).sub.5                                                                             365          85                                                    CuBi(CN).sub.5                                                                             324          78                                                    FeBi(SCN).sub.5                                                                            315          87                                                    BaBi(ONC).sub.5                                                                            320          83                                                    CaBi(CN).sub.3                                                                             321          77                                                    MgBi(CN).sub.3                                                                             315          78                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 8.

The batteries using the metal or semi-metal cyanide, cyanate, or thiocyanate of Example 8 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 9

The electrode characteristics of various metal and semi-metal tungstates specified in Table 31 and used as the anode active material were evaluated in Example 9.

Table 31 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 31                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.3 (WO.sub.4).sub.3                                                                  292          86                                                    AlWO.sub.4  301          83                                                    SnWO.sub.4  477          94                                                    Sn.sub.2 W.sub.3 O.sub.8                                                                   436          95                                                    Sn(WO.sub.4).sub.2                                                                         402          96                                                    Si(WO.sub.4).sub.2                                                                         282          95                                                    PbWO.sub.4  405          95                                                    PbWO.sub.3  419          94                                                    CdWO.sub.4  326          91                                                    CdWO.sub.3  345          90                                                    Bi.sub.2 WO.sub.6                                                                          382          90                                                    Bi.sub.2 (WO.sub.4).sub.3                                                                  368          92                                                    In.sub.2 (WO.sub.4).sub.3                                                                  426          90                                                    In(WO.sub.3).sub.3                                                                         398          94                                                    Sb.sub.2 (WO.sub.4).sub.3                                                                  350          90                                                    ZnWO.sub.4  208          86                                                    ZnWO.sub.3  226          89                                                    Ga.sub.2 (WO.sub.4).sub.3                                                                  321          89                                                    Ga.sub.2 (WO.sub.3).sub.3                                                                  333          88                                                    Ge(WO.sub.4).sub.2                                                                         341          89                                                    Ge(WO.sub.3).sub.2                                                                         353          86                                                    MgWO.sub.4  301          87                                                    MgWO.sub.3  313          86                                                    CaWO.sub.4  301          87                                                    CaWO.sub.3  313          86                                                    SrWO.sub.4  301          87                                                    SrWO.sub.3  313          86                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 9.

The batteries using the metal or semi-metal tungstate of Example 9 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 10

The electrode characteristics of various metal and semi-metal molybdates specified in Table 32 and used as the anode active material were evaluated in Example 10.

Table 32 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 32                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (MoO.sub.4).sub.3                                                                 302          87                                                    SnMo.sub.2 O.sub.8                                                                         426          94                                                    SnMoO.sub.4 472          92                                                    SiMo.sub.2 O.sub.8                                                                         340          90                                                    PbMoO.sub.4 456          94                                                    CdMoO.sub.4 346          91                                                    Bi.sub.2 (MoO.sub.4).sub.3                                                                 402          93                                                    In.sub.2 (MoO.sub.4).sub.3                                                                 436          94                                                    InMo.sub.4 O.sub.6                                                                         398          96                                                    Sb.sub.2 (MoO.sub.4).sub.3                                                                 348          90                                                    ZnMoO.sub.4 268          87                                                    Ga.sub.2 (MoO.sub.4).sub.3                                                                 359          89                                                    GeMoO.sub.4 371          90                                                    MgMoO.sub.4 324          88                                                    CaMoO.sub.4 324          88                                                    SrMoO.sub.4 324          88                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 10.

The batteries using the metal or semi-metal molybdate of Example 10 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 11

The electrode characteristics of various metal and semi-metal titanates specified in Table 33 and used as the anode active material were evaluated in Example 11.

Table 33 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 33                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         AlTiO.sub.5 326          73                                                    SnTiO.sub.4 443          82                                                    SiTiO.sub.6 321          75                                                    PbTiO.sub.3 476          80                                                    PbTi.sub.3 O.sub.7                                                                         402          81                                                    CdTiO.sub.3 354          76                                                    Bi.sub.2 TiO.sub.5                                                                         498          81                                                    Bi.sub.2 Ti.sub.2 O.sub.7                                                                  424          82                                                    In.sub.2 TiO.sub.5                                                                         478          83                                                    Sb.sub.3 Ti.sub.2 O.sub.10                                                                 369          80                                                    ZnTiO.sub.3 324          76                                                    GaTiO.sub.5 371          75                                                    GeTiO.sub.3 380          74                                                    MgTiO.sub.4 334          71                                                    CaTiO.sub.4 334          71                                                    SrTiO.sub.4 334          71                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 11.

The batteries using the metal or semi-metal titanate of Example 11 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 12

The electrode characteristics of various metal and semi-metal zirconates specified in Table 34 and used as the anode active material were evaluated in Example 12.

Table 34 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 34                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 (ZrO.sub.3).sub.3                                                                 304          71                                                    SnZrO.sub.3 484          78                                                    SiZrO.sub.4 342          76                                                    PbZrO.sub.3 466          77                                                    CdZrO.sub.3 357          71                                                    Bi.sub.2 (ZrO.sub.3).sub.3                                                                 419          77                                                    In.sub.2 (ZrO.sub.3).sub.3                                                                 443          78                                                    Sb.sub.2 (ZrO.sub.3).sub.3                                                                 354          75                                                    ZnZrO.sub.3 294          73                                                    Ga.sub.2 (ZrO.sub.3).sub.3                                                                 372          74                                                    GeZrO.sub.3 379          72                                                    MgZrO.sub.3 339          73                                                    CaZrO.sub.3 339          73                                                    SrZrO.sub.3 339          73                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 12.

The batteries using the metal or semi-metal zirconate of Example 12 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 13

The electrode characteristics of various metal and semi-metal vanadates specified in Table 35 and used as the anode active material were evaluated in Example 13.

Table 35 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 35                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         AlVO.sub.4  319          82                                                    SnV.sub.2 O.sub.6                                                                          452          89                                                    Sn.sub.2 V.sub.2 O.sub.6                                                                   489          87                                                    SiV.sub.2 O.sub.7                                                                          324          84                                                    Pb.sub.2 V.sub.2 O.sub.6                                                                   477          86                                                    PbV.sub.2 O.sub.6                                                                          427          88                                                    CdV.sub.2 O.sub.6                                                                          326          83                                                    BiVO.sub.4  436          86                                                    Bi.sub.2 VO.sub.5                                                                          496          85                                                    InVO.sub.4  498          85                                                    In.sub.2 VO.sub.5                                                                          504          83                                                    SbVO.sub.4  354          83                                                    ZnV.sub.2 O.sub.6                                                                          311          81                                                    GaVO.sub.4  368          83                                                    GeV.sub.2 O.sub.6                                                                          341          84                                                    MgV.sub.2 O.sub.6                                                                          312          79                                                    CaV.sub.2 O.sub.6                                                                          312          79                                                    SrV.sub.2 O.sub.6                                                                          312          79                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 13.

The batteries using the metal or semi-metal vanadate of Example 13 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 14

The electrode characteristics of various metal and semi-metal chromates specified in Table 36 and used as the anode active material were evaluated in Example 14.

Table 36 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 36                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         AlCrO.sub.3 342          87                                                    SnCrO.sub.4 463          94                                                    Sn.sub.2 CrO.sub.6                                                                         504          92                                                    Si(CrO.sub.4).sub.2                                                                        341          89                                                    Pb.sub.3 CrO.sub.6                                                                         511          91                                                    PbCrO.sub.4 484          93                                                    CdCr.sub.2 O.sub.4                                                                         324          87                                                    BiCrO.sub.3 432          91                                                    Bi.sub.2 CrO.sub.6                                                                         426          93                                                    InCrO.sub.3 445          92                                                    In.sub.2 CrO.sub.6                                                                         486          90                                                    Sb.sub.2 (CrO.sub.4).sub.3                                                                 352          88                                                    ZnCrO.sub.4 336          87                                                    Ga.sub.3 (CrO.sub.4).sub.2                                                                 381          86                                                    GeCrO.sub.4 382          85                                                    MgCr.sub.2 O.sub.7                                                                         304          87                                                    CaCr.sub.2 O.sub.7                                                                         304          87                                                    SrCr.sub.2 O.sub.7                                                                         304          87                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 14.

The batteries using the metal or semi-metal chromate of Example 14 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 15

The electrode characteristics of various metal and semi-metal niobates specified in Table 37 and used as the anode active material were evaluated in Example 15.

Table 37 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 37                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         AlNbO.sub.4 324          71                                                    SnNb.sub.2 O.sub.6                                                                         424          75                                                    Sn.sub.2 Nb.sub.2 O.sub.7                                                                  468          74                                                    SiNbO.sub.4 342          71                                                    PbNb.sub.2 O.sub.6                                                                         403          74                                                    Pb.sub.2 Nb.sub.2 O.sub.7                                                                  426          72                                                    Cd.sub.2 Nb.sub.2 O.sub.7                                                                  314          71                                                    BiNbO.sub.4 415          73                                                    InNbO.sub.4 445          74                                                    SbNbO.sub.4 370          73                                                    ZnNb.sub.2 O.sub.6                                                                         204          71                                                    GaNbO.sub.4 364          72                                                    GeNb.sub.2 O.sub.6                                                                         368          73                                                    MgNb.sub.2 O.sub.6                                                                         301          72                                                    CaNb.sub.2 O.sub.6                                                                         301          72                                                    SrNb.sub.2 O.sub.6                                                                         301          72                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 15.

The batteries using the metal or semi-metal niobate of Example 15 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 16

The electrode characteristics of various metal and semi-metal tantalates specified in Table 38 and used as the anode active material were evaluated in Example 16.

Table 38 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 38                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         AlTaO.sub.4 302          81                                                    Sn.sub.2 Ta.sub.2 O.sub.7                                                                  476          88                                                    SiTa.sub.2 O.sub.7                                                                         272          82                                                    Pb.sub.2 Ta.sub.2 O.sub.7                                                                  406          87                                                    Cd.sub.2 Ta.sub.2 O.sub.7                                                                  314          84                                                    BiTaO.sub.4 404          86                                                    InTaO.sub.4 446          85                                                    SbTaO.sub.4 364          85                                                    Zn.sub.2 Ta.sub.2 O.sub.7                                                                  246          83                                                    GaTaO.sub.4 356          81                                                    Ge.sub.2 Ta.sub.2 O.sub.7                                                                  346          81                                                    Mg.sub.2 Ta.sub.2 O.sub.7                                                                  304          79                                                    Ca.sub.2 Ta.sub.2 O.sub.7                                                                  304          79                                                    Sr.sub.2 Ta.sub.2 O.sub.7                                                                  304          79                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 16.

The batteries using the metal or semi-metal tantalate of Example 16 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

EXAMPLE 17

The electrode characteristics of various metal and semi-metal manganates specified in Table 39 and used as the anode active material were evaluated in Example 17.

Table 39 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1.

                  TABLE 39                                                         ______________________________________                                                                  Capacity                                                          Discharge capacity                                                                          maintenance rate                                      Salt        (mAh/g)      (%)                                                   ______________________________________                                         Al.sub.2 MnO.sub.6                                                                         326          80                                                    SnMnO.sub.3 486          89                                                    SnMn.sub.2 O.sub.4                                                                         424          90                                                    SiMnO.sub.3 314          81                                                    PbMnO.sub.3 443          87                                                    CdMnO.sub.3 369          82                                                    Bi.sub.2 MnO.sub.4                                                                         424          84                                                    Bi.sub.2 MnO.sub.6                                                                         412          86                                                    In.sub.2 MnO.sub.4                                                                         461          84                                                    In.sub.2 MnO.sub.6                                                                         452          84                                                    Sb.sub.2 MnO.sub.4                                                                         392          83                                                    Sb.sub.2 MnO.sub.6                                                                         376          84                                                    ZnMnO.sub.3 314          81                                                    Ga.sub.2 MnO.sub.4                                                                         386          81                                                    GeMnO.sub.3 349          82                                                    MgMnO.sub.3 326          78                                                    CaMnO.sub.3 326          78                                                    SrMnO.sub.3 326          78                                                    ______________________________________                                    

After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 17.

The batteries using the metal or semi-metal manganate of Example 17 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides.

Although all the above examples refer to the cylindrical batteries, the principle of the present invention is not restricted to this structure but may be applicable to secondary batteries of various types, such as coin-type, rectangular-type, and cylinder-type.

In the above examples, LiMn₁.8 Co₀.2 O₄ was used as the cathode active material. The similar effects can be exerted for a variety of other cathode active materials allowing reversible charge and discharge operations, such as LiMn₂ O₄, LiCoO₂, LiNiO₂, and the like.

As discussed above, the present invention uses an anode of high capacity and excellent cycle life and thereby provides a non-aqueous electrolyte secondary battery that is free of a short circuit due to dendrite and has a higher energy density and a high reliability.

Although the present invention has been described in terms of the presently preferred embodiments, it is to be understood that such disclosure is not to be interpreted as limiting. Various alterations and modifications will no doubt become apparent to those skilled in the art to which the present invention pertains, after having read the above disclosure. Accordingly, it is intended that the appended claims be interpreted as covering all alterations and modifications as fall within the true spirit and scope of the invention. 

What is claimed is:
 1. A non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, said anode having an active material that comprises a salt of a metal or a semi-metal and a compound selected from the group consisting of oxo-acids, thiocyanic acid, cyanogen, and cyanic acid, wherein each said oxo-acid comprises an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates.
 2. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said anode comprises a mixture of said active material, carbon material, and a binding agent.
 3. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal or semi-metal is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Sr, B, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb.
 4. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of nitrogen is at least one selected from the group consisting of nitrates and nitrites.
 5. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of sulfur is at least one selected from the group consisting of sulfates, sulfites, disulfates, peroxomonosulfates, peroxodisulfates, thiosulfates, dithionates, disulfites, thiosulfites, dithionites, and sulfoxylates.
 6. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of phosphorus is at least one selected from the group consisting of monohydrogenphosphates, dihydrogenphosphates, phosphinates, and phosphonates.
 7. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of boron is at least one selected from the group consisting of monohydrogenborates and dihydrogenborates.
 8. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of selenium is at least one selected from the group consisting of selenates M₂ (SeO₄)_(m), selenites M₂ (SeO₃)_(m), M₂ (SeO₅)_(m), M(HSeO₄)_(m), and M(HSeO₃)_(m), where M denotes a metal or semi-metal having a valence m.
 9. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of tellurium is at least one selected from the group consisting of M₆ (TeO₆)_(m), M₂ (TeO₄)_(m), M₅ (H₅ TeO₆), M₄ (H₂ TeO₆)_(m), M₂ (H₃ TeO₆)_(m), and M₂ (H₄ TeO₆)_(m), where M denotes a metal or semi-metal having a valence m.
 10. A non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, said anode having an active material that comprises a salt of a metal or a semi-metal and an oxo-acid of an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, and tellurium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates.
 11. The non-aqueous electrolyte secondary battery in accordance with claim 10, wherein said metal or semi-metal is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Sr, B, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb.
 12. A non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, said anode having an active material that comprises a salt of a metal or a semi-metal and an oxo-acid of a transition element selected from the group consisting of tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium.
 13. The non-aqueous electrolyte secondary battery in accordance with claim 12, wherein said metal or semi-metal is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Sr, B, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb.
 14. A non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, said anode having an active material that comprises a salt of a metal or a semi-metal and an oxo-acid, wherein said metal or semi-metal is at least one selected from the group consisting of Sn and Si, wherein said oxo-acid comprises an element selected from the group consisting of sulfur, phosphorus and boron and wherein salts of said oxo-acids of phosphorus and boron are restricted to hydrogenphosphates and hydrogenborates. 